CN1117404A - Catalyst and method for converting heavy arene into light one - Google Patents
Catalyst and method for converting heavy arene into light one Download PDFInfo
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- CN1117404A CN1117404A CN94114962A CN94114962A CN1117404A CN 1117404 A CN1117404 A CN 1117404A CN 94114962 A CN94114962 A CN 94114962A CN 94114962 A CN94114962 A CN 94114962A CN 1117404 A CN1117404 A CN 1117404A
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Abstract
The catalyst for prepn. of benzene, toluene and xylol from 9 C arene material uses (wt.%) 30-70 of ZSM-5 zeolite and 30-70 of gammar-or eta-Al2O3 as carrier, and 0.1-0.5 of Re, 0.1-0.5 of Sn, 0.05-0.3 of Pt or 0.2-0.8 of Pd as load. Under the operation condition 350-450 deg.C, 0.5-3.5 MPa, wt. space rate 1-5 per hour, hydrogen/hydrocarbon volume ratio 500-1200, the catalyst has higher activity and stability and lower hydrogen consumption as compared with prior art.
Description
The invention relates to the method that a kind of catalyst, this Preparation of catalysts method and this catalyst that is used for heavy aromatic hydrocarbon light is used for heavy aromatic hydrocarbon light.Specifically, the invention relates to and a kind ofly contain catalyst, this Preparation of catalysts method and this catalyst synthesizing Si-Al hydrochlorate zeolite and noble metal, that be used for the heavy aromatic hydrocarbon light more than nine carbon atoms is produced benzene, toluene and dimethylbenzene (following brief note is BTX) and be used for the process that above-mentioned heavy arene makes it lighting.
Heavy arene mainly is present in the catalytic reforming products therefrom and hydrocarbon cracking is produced in the ethene gained drippolene.According to statistics, nearly 800,000 tons of heavy arene was produced in the whole nation in 1993, and except that seldom a part is as the solvent, all the other have all used as fuel, and estimate that the growing amount of annual heavy arene also will increase to some extent from now on.Therefore how heavy arene effectively being fully utilized is an important topic to be solved, and China's research work in this respect is still blank.
At USP4, once disclosed a technology that ethylbenzene and the alkylbenzene more than eight carbon atom is converted into BTX in 341,622.This process using contain zeolite and have the low acid active catalyst of the metal of hydrogenation/dehydrogenation activity, when 800～1000 (427～540 ℃), 200psig, liquid hourly space velocity (LHSV) 5
-1Reaction condition under the side chain of two or more carbon atoms is removed from phenyl ring, the realization ethylbenzene conversion is that benzene, first and second benzene are converted into toluene, dimethyl ethyl benzene is converted into reactions such as dimethylbenzene.The zeolite that uses in this catalyst for restrictive index 1～12, aperture greater than 5A, silica alumina ratio at least 12, greater than 200 better, greater than 500 best crystalline aluminosilicates, as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38 etc.The metal constituent element with hydrogenation/dehydrogenation activity that uses in the catalyst is selected from the VIII metalloid, preferably precious metals pt, Pd.For example with C
9 +Arene content is that the industrial reformate more than 305 of 89.4 heavy % is when being raw material, when 900 (480 ℃), 200psig, weight (hourly) space velocity (WHSV) 10
-1, hydrogen/hydrocarbon (mol ratio) 5 condition under, will consist of ZSM-5, the Al of 35 heavy % of the silica alumina ratio 1600 of 65 heavy %
2O
3, 0.1 heavy % the catalyst of Pt contact with raw material hydrocarbon, institute's amount of benzene, toluene and the dimethylbenzene of generation only accounts for 3.62～4.25 heavy %, 14.92～17.42 heavy % and 6.47～7.64 weight % of raw material gross weight respectively, by C
8 -Clean growing amount of aromatic hydrocarbons and C
9 +It is 70～73% that feed stock conversion is compared the selectivity that is calculated.
USP5 has disclosed the catalysis process of an alkyl aromatic compound hydro-dealkylation in 001,296.Used in this method and contained silica alumina ratio, in 600～1000 (315～540 ℃), 50～500psig, liquid hourly space velocity (LHSV) 0.5～10 o'clock greater than 10 the MCM-22 zeolite and the catalyst of noble metal or nickel
-1, hydrogen cycle rate 50～5000 standard Foot
3Under the reaction condition of/barrel, with C
6～12Mononuclear aromatics＞50 mole %, C
9～12The raw material hydrodealkylation of mononuclear aromatics＞50 mole % is made BTX.For example with C
9 +Arene content is that the raw material of 96.8 moles of % is when 600～900 (315～480 ℃), 200psig, liquid hourly space velocity (LHSV) 2.5
-1, hydrogen internal circulating load 2000 standard Foot
3Weigh the Al of % under the condition of/barrel with the MCM-22 zeolite that consists of 65 heavy %, 35
2O
3, 0.66 heavy % the catalyst contact of Pt, the amount of benzene, toluene and dimethylbenzene is respectively 16.0～45.8 moles, 2.7～15.4 moles and 7.8～24.1 moles in the products therefrom, the selectivity of BTX is 63.8～80.9 moles of %.
At USP5,001,296 continuation-in-part application USP5 has also disclosed the catalysis conversion method that the same hydrocarbon feed hydro-dealkylation that contains alkyl aromatic compound is produced BTX in 043,513.
The objective of the invention is on the basis of existing technology: one. provide one to have more high activity and new catalyst activity stability, that be used for the heavy aromatic hydrocarbon light that (comprises nine carbon atoms) more than nine carbon atoms is produced BTX; Two. this Preparation of catalysts method is provided; Three. provide this catalyst to be used for the technology that heavy aromatic hydrocarbon light is produced BTX.
Catalyst provided by the invention is with ZSM-5 zeolite and γ-or η-Al
2O
3, preferably ZSM-5 and γ-Al
2O
3Be carrier, load Re, Sn and Pt or Pd constitute.The ZSM-5 zeolite accounts for 30～70 heavy % (in vehicle weight, down together), best 40～60 heavy % in the carrier; Al
2O
3Account for 30～70 heavy %, best 40～60 heavy %.The carried metal amount is 0.1～0.5 heavy %Re, 0.1～0.5 heavy %Sn, 0.05～0.3 heavy %Pt or 0.2～0.8 heavy %Pd.
This Preparation of catalysts method provided by the invention is as follows:
With sodium type ZSM-5 zeolite and Al
2O
3Or its precursor predetermined amounts mixes, add aqueous solution of nitric acid mix pinch, moulding, roasting make carrier; With ammonium salt aqueous solution carrier being carried out ion-exchange treatment reaches more than 90% the exchange degree of sodium ion in the ZSM-5 zeolite; Mixed liquor dipping and roasting with each metal component precursor of Re, Sn, Pt or Pd.
Its concrete preparation process is:
1. the preparation of carrier: with sodium type ZSM-5 zeolite and Al
2O
3Or its precursor predetermined amounts mixes, add mixed powder weight 25～60%, best 35～45%, concentration be the aqueous solution of nitric acid of 1～5 heavy %, best 1.5～3.0 heavy % mix pinch, moulding, drying, 450～650 ℃, best 500～600 ℃ of following roastings are 2～8 hours, best 3～6 hours in the air.
2. ammonium ion exchange: room temperature to 120 ℃, best 85～100 ℃ down with the NH that are selected from of 0.1～0.8N, best 0.2～0.6N
4Cl or NH
4NO
3Ammonium salt above-mentioned carrier is carried out ion-exchange, each 1～6 hour, best 1～3 hour, Na in the Na-ZSM-5 zeolite
+Exchange degree reach more than 90% filtration, washing, drying.
3. the introducing of metal component: under the condition of room temperature, liquid-solid ratio 1～3, flood carrier 8～60 hours after the above-mentioned ammonium ion exchange, best 12～36 hours with the mixed liquor of each metal component precursor, filter, drying, 400～600 ℃, best 450～550 ℃ of roastings are 1～10 hour, best 3～6 hours in the air.
Metal component Sn also can be by direct impregnation in advance at Al
2O
3Or the mode on its precursor is introduced catalyst.
Used ZSM-5 zeolite can be included amine method and non-amine method and be made by known technology arbitrarily in this catalyst, and its silica alumina ratio is preferably 15～150, and crystal grain should be less than 1 micron.Al
2O
3Precursor be the various hydrated aluminas that comprise amorphous hydroted alumina; Al
2O
3System is made by the hydrated alumina heating that various known technologies make, preferably according to the disclosed γ-Al that is made by the low-carbon alkoxy aluminium Hydrolyze method in CN 85100218 patents
2O
3The precursor of used metal component is the precursor of being used always in the catalyst preparation technology among the present invention, as chloroplatinic acid, palladium bichloride, perrhenic acid, stannous chloride.
Catalyst provided by the invention is used for heavy aromatic hydrocarbon light and produces the method for BTX and be: will contain C
9 +The hydrocarbon feed of aromatic hydrocarbons contacts with this catalyst under the condition of 350～450 ℃ of reaction temperatures, reaction pressure 0.5～3.5MPa, weight space velocity 1～5 o'clock, hydrogen/hydrocarbon (volume ratio) 500～1200, reclaims products therefrom and separates.
It is high activity that heavy arene is transformed and the growing amount of BTX that catalyst provided by the invention has than the prior art catalyst.For example under identical reaction condition to C
9 +Arene content is the heavy arenes of 97.95 heavy % when transforming, and the growing amount that the invention provides activity of such catalysts and BTX all is 2～6 times of prior art catalyst.
Catalyst provided by the invention also has the characteristics that activity stability is good, the hydrogen consumption is little, for example to C
9 +Arene content is the heavy arenes of 97.95 heavy % when transforming, and react after 1000 hours, and the carbon deposit on the catalyst just has 6.1 heavy %, and the hydrogen consumption only is 2.3 weight %.
In the Preparation of catalysts method provided by the invention zeolite has been adopted the flow process of ion-exchange after the first moulding, this flow process is compared with habitual usually in the art first ion-exchange aftershaping flow process, promptly reduced the loss of exchange process mesolite, improved the yield of zeolite, reduced the pollution of dust again to environment, and having shortened the required time of filtration washing greatly, this is particularly remarkable for large-scale production.
Catalyst provided by the invention is used for heavy arene and transforms when making BTX, and desired reaction temperature is low than prior art, and each operating parameter all can change in relative broad range.
Following example will give further instruction to the present invention.
Example 1～4
Preparation of catalysts provided by the invention
With a certain amount of ZSM-5 zeolite (dying of Shanghai seven factory's products, crystal grain is less than 1 micron) and a certain amount of Al
2O
3(γ-Al
2O
3System is prepared into η-Al by the method described in the CN 85100218
2O
3Be Fushun No.3 Petroleum Factory's industrial products) mix, add powder weight 40%, concentration be 2% aqueous solution of nitric acid mix pinch, extruded moulding, 110～120 ℃ of dryings, 550 ℃ of roastings promptly got carrier in 4 hours in the air.
Get the above-mentioned 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, filtered washing, 110～120 ℃ of dryings.
Under the condition of room temperature, liquid-solid ratio 2, flood carrier 24 hours after the above-mentioned ammonium ion exchange with the mixed liquor of each metal component precursor of scheduled volume, filter 110～120 ℃ of dryings, 500 ℃ of roastings promptly got catalyst sample in 4 hours in the air, and note is made catalyst A, B, C, D respectively.
Used metal component precursor chloroplatinic acid and perrhenic acid all are Fushun No.3 Petroleum Factory's product, and used the two concentration is respectively 2.86 mg/ml and 11.8 mg/ml in the example.Palladium bichloride is the Guangzhou Chemical Reagent Factory product, during use with dissolving with hydrochloric acid and be mixed with the solution that concentration is 1 heavy %.Stannous chloride is Beijing Chemical Plant's product, analyze pure, water dissolving and be mixed with the solution that concentration is 1 heavy % during use.
Table 1 has been listed above-mentioned catalyst sample related parameter, wherein ZSM-5 zeolite and Al
2O
3Consumption and the last amount of metal active constituent all be to be the percetage by weight of benchmark in the carrier.
For embodiment the invention provides the characteristics of catalyst, according to USP4, the content disclosed in 341,622 is the catalyst sample agent as a comparison that 500 ZSM-5 zeolite has been made supporting Pt with silica alumina ratio, has related parameter to list in table 1 in the lump.
Table 1
| Example | ????1 | ????2 | ????3 | ????4 | Contrast |
| ZSM-5 zeolite silica alumina ratio consumption, heavy % Al 2O 3The crystal formation consumption, heavy % metal impregnation amount, heavy % Pt Pd Re Sn | ? ????60 ????40 ? ????γ ????????60 ? ????0.05 ????0.0 ????0.10 ????0.12 | ? ????60 ????60 ? ????γ ????????40 ? ????0.05 ????0.0 ????0.10 ????0.12 | ? ????60 ????60 ? ????γ ????????40 ? ????0.10 ????0.0 ????0.15 ????0.12 | ? ????60 ????60 ? ????η ????????40 ? ????0.0 ????0.5 ????0.10 ????0.12 | ? ????500 ????60 ? ????γ ????????40 ? ????0.10 ????0.0 ????0.0 ????0.0 |
| The catalyst numbering | ????A | ????B | ????C | ????D | Contrast |
Example 5～7
Preparation of catalysts provided by the invention
γ-the Al of vehicle weight 40% will be accounted for
2O
3Powder is used the SnCl of scheduled volume under the condition of room temperature, liquid-solid ratio 2
2Solution impregnation 15 hours will be soaked 110～120 ℃ of evaporates to dryness of surplus liquid, and the ZSM-5 zeolite that adds vehicle weight 60% mixes, again according to method HNO described in the example 1～4
3Peptization, moulding, make carrier, after ammonium ion exchange,, make catalyst sample E, F, G with the chloroplatinic acid and the perrhenic acid dipping of scheduled volume.
Table 2 has been listed above-mentioned catalyst sample related parameter.
Table 2
| Example | ????5 | ????6 | ????7 |
| ZSM-5 zeolite silica alumina ratio Al 2O 3Soak the Sn amount, heavy % metal impregnation amount, heavy % Pt Re | ????60 ????0.12 ? ????0.05 ????0.10 | ????120 ????0.35 ? ????0.20 ????0.40 | ????25 ????0.12 ? ????0.05 ????0.10 |
| The catalyst numbering | ????E | ????F | ????G |
Example 8
Catalyst provided by the invention can be applied to C in certain process conditions scope
9 +The lighting of heavy arene.
Pay with reformation in the factory, disproportionation and isomerization and to produce heavy arene (C wherein
9 +Arene content is 97.95 heavy %) for raw material, when 400 ℃ of reaction temperatures, reaction pressure 1.0MPa, weight space velocity 2.0
-1, hydrogen/hydrocarbon (volume ratio) 1000 condition under catalyst provided by the invention and comparative catalyst are estimated.Evaluation response carries out on 10 milliliters of reaction units, and the catalyst loading amount is 5 grams, and hydrogen once passes through.Gained the results are shown in table 3.
Under different technology conditions, to the invention provides the table 4 that the results are shown in that catalyst estimates.
In the table: C
9 +Aromatics conversion rate, heavy %=
(heavy %) is as follows for raw materials used composition: C
8 -Alkane and cycloalkane 0.47; C
8Aromatic hydrocarbons 1.58; C
9Aromatic hydrocarbons 21.42; C
10Aromatic hydrocarbons 44.73; C
11Aromatic hydrocarbons 13.80; C
12 +Aromatic hydrocarbons 18.00.
By table 3 and table 4 data as can be known: the invention provides catalyst and can in certain process conditions scope, be applied to the lighting of heavy arene, and to obtain than prior art be high to C
9 +The conversion ratio of aromatic hydrocarbons and the growing amount of BTX.
Table 3
| Catalyst | ????A | ????C | ????G | Contrast |
| Product distributes, heavy % C 8 -Alkane and cycloalkanes benzene (B) toluene (T) dimethylbenzene (X) | ? ????3.0 ????3.7 ????7.0 ????12.2 | ? ????2.2 ????4.0 ????8.2 ????13.0 | ? ????2.4 ????6.8 ????23.5 ????32.4 | ? ????1.0 ????2.0 ????4.1 ????6.3 |
| C 9 +Aromatics conversion rate, heavy % BTX growing amount, heavy % | ????24.3 ????22.9 | ????25.7 ????25.2 | ????64.3 ????62.7 | ????11.4 ????10.8 |
Table 4
| Catalyst | ??B | ??B | ??D | ??E | ??F |
| The process conditions reaction temperature, ℃ reaction pressure, the MPa weight space velocity, the time -1Hydrogen/hydrocarbon (volume ratio) | ? ??390 ??1.0 ??2 ??1000 | ? ??390 ??1.0 ??4 ??1000 | ? ??390 ??1.0 ??2 ??1000 | ? ??390 ??1.5 ??2 ??1000 | ? ??430 ??3.0 ??2 ??600 |
| Product distributes, heavy % C 8 -Alkane and cycloalkanes benzene (B) toluene (T) dimethylbenzene (X) | ? ??2.3 ??4.3 ??8.4 ??13.8 | ? ??2.0 ??4.1 ??8.2 ??13.0 | ? ??3.1 ??4.4 ??8.5 ??14.1 | ? ??3.0 ??4.4 ??8.6 ??14.2 | ? ??5.1 ??6.5 ??16.3 ??17.0 |
| C 9 +Aromatics conversion rate, heavy % BTX growing amount, heavy % | ??27.2 ??26.5 | ??25.6 ??25.3 | ??28.5 ??27.0 | ??28.6 ??27.2 | ??43.6 ??39.8 |
Example 9
Catalyst provided by the invention has higher activity stability and lower hydrogen consumption.
On 50 milliliters medium-sized reaction unit, 390～400 ℃, when 1.0～1.3MPa, weight space velocity 2
-1, hydrogen/hydrocarbon (volume ratio) 1000 condition under, with catalyst E to forming the same C
9 +Heavy arene carries out the activity stability test, and the catalyst loading amount is 20 grams.(heavy %) is as follows for the composition of product: C
8 -Alkane and cycloalkanes 3.4; Benzene 4.7; Toluene 8.2; Ethylbenzene 0.1; Paraxylene 2.9; Meta-xylene 6.6; Ortho-xylene 2.7.C
9 +Aromatics conversion rate is 27.0 heavy %; BTX growing amount 25.2 heavy %.1000 hours continuously the carbon deposit on the running rear catalyst 6.1 heavy % are only arranged, the hydrogen consumption only is 2.3 heavy %.
Claims (9)
1. catalyst that contains ZSM-5 zeolite, aluminium oxide and VIII class noble metal is characterized in that this catalyst is in the ZSM-5 zeolite of 30～70 heavy % (is benchmark with the carrier, down with) and the γ of 30～70 heavy %-or η-Al
2O
3Be carrier, the Pd of the Pt of the Re of load 0.1～0.5 heavy %, the Sn of 0.1～0.5 heavy %, 0.05～0.3 heavy % or 0.2～0.8 heavy % forms.
2. according to the said catalyst of claim 1, it is characterized in that this catalyst is with the ZSM-5 zeolite of 40～60 heavy % and the γ of 40～60 heavy %-or η-Al
2O
3For carrier is formed.
3. according to claim 1 or 2 said catalyst, it is characterized in that this catalyst is with ZSM-5 zeolite and γ-Al
2O
3For carrier is formed.
4. a Preparation of catalysts method according to claim 1 is characterized in that: with sodium type ZSM-5 zeolite and Al
2O
3Or its precursor predetermined amounts mixes, add aqueous solution of nitric acid mix pinch, moulding, roasting make carrier; With ammonium salt aqueous solution carrier being carried out ion-exchange treatment reaches more than 90% the exchange degree of the sodium ion in the ZSM-5 zeolite; Mixed liquor dipping and roasting with each metal component precursor of Re, Sn, Pt or Pd.
5. according to the said preparation method of claim 4, the silica alumina ratio that it is characterized in that ZSM-5 zeolite wherein is 15～150, and crystal grain is less than 1 micron.
6. according to the said preparation method of claim 4, it is characterized in that Al wherein
2O
3Be to make by the hydrated alumina heating that various known technologies make.
7. according to the said preparation method of claim 4, it is characterized in that Al wherein
2O
3Be the γ-Al that makes by the low-carbon alkoxy aluminium Hydrolyze method
2O
3
8. according to the said preparation method of claim 4, it is characterized in that wherein the Sn component in advance direct impregnation at Al
2O
3Or on its precursor.
One kind with the described catalyst of claim 1 by containing C
9 +The hydrocarbon feed of aromatic hydrocarbons is produced the method for benzene, toluene and dimethylbenzene, it is characterized in that: with hydrocarbon feed in 350～450 ℃ of reaction temperatures, reaction pressure 0.5～3.5MPa, weight space velocity 1～5 o'clock
-1, hydrogen/hydrocarbon (volume ratio) 500～1200 condition under contact with this catalyst.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114962A CN1048425C (en) | 1994-08-22 | 1994-08-22 | Catalyst and method for converting heavy arene into light one |
| TW085100869A TW408033B (en) | 1994-08-22 | 1996-01-25 | A catalyst for the conversion of heavy aromatics to light aromatics and a process for the same conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94114962A CN1048425C (en) | 1994-08-22 | 1994-08-22 | Catalyst and method for converting heavy arene into light one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117404A true CN1117404A (en) | 1996-02-28 |
| CN1048425C CN1048425C (en) | 2000-01-19 |
Family
ID=5037299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94114962A Expired - Lifetime CN1048425C (en) | 1994-08-22 | 1994-08-22 | Catalyst and method for converting heavy arene into light one |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1048425C (en) |
| TW (1) | TW408033B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082539C (en) * | 1999-04-16 | 2002-04-10 | 中国石油化工集团公司 | Heavy arene lightening catalyst and the separating method of lightened product |
| CN101734986A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline |
| CN101348405B (en) * | 2007-07-18 | 2011-01-19 | 中国石油化工股份有限公司 | Method for preparing light arene and light alkane from hydrocarbon raw material |
| CN101607207B (en) * | 2008-06-19 | 2011-06-22 | 中国石油天然气股份有限公司 | Heavy aromatic hydrocarbon lightening catalyst and preparation method and application thereof |
| CN101348733B (en) * | 2007-07-18 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing light arene and light alkane from hydrocarbon raw material |
| CN104174428A (en) * | 2013-05-22 | 2014-12-03 | 中国石油化工股份有限公司 | Catalyst and method for lightening C9<+> heavy aromatics by use of catalyst |
| CN108786902A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of heavy aromatics conversion catalyst and preparation method thereof |
| CN109395727A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics lightening catalyst |
| CN115193471A (en) * | 2022-05-11 | 2022-10-18 | 中海油天津化工研究设计院有限公司 | Hydrocracking catalyst for distillate oil containing heavy aromatics and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404129C (en) * | 2005-10-25 | 2008-07-23 | 中国石油天然气股份有限公司 | Catalyst for removing hydrocarbon impurities in carbon dioxide, preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4341622A (en) * | 1980-12-04 | 1982-07-27 | Mobil Oil Corporation | Manufacture of benzene, toluene and xylene |
| CN1029612C (en) * | 1988-10-17 | 1995-08-30 | 美国环球油品公司 | Aromatic hydrocarbon isomerization method |
| JP2598127B2 (en) * | 1989-03-29 | 1997-04-09 | 帝人株式会社 | Xylene isomerization method |
| US5001296A (en) * | 1990-03-07 | 1991-03-19 | Mobil Oil Corp. | Catalytic hydrodealkylation of aromatics |
| CN1026244C (en) * | 1991-12-12 | 1994-10-19 | 中国石油化工总公司石油化工科学研究院 | Catalytic reforming method for hydrocarbon oil |
-
1994
- 1994-08-22 CN CN94114962A patent/CN1048425C/en not_active Expired - Lifetime
-
1996
- 1996-01-25 TW TW085100869A patent/TW408033B/en not_active IP Right Cessation
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082539C (en) * | 1999-04-16 | 2002-04-10 | 中国石油化工集团公司 | Heavy arene lightening catalyst and the separating method of lightened product |
| CN101348405B (en) * | 2007-07-18 | 2011-01-19 | 中国石油化工股份有限公司 | Method for preparing light arene and light alkane from hydrocarbon raw material |
| CN101348733B (en) * | 2007-07-18 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing light arene and light alkane from hydrocarbon raw material |
| CN101607207B (en) * | 2008-06-19 | 2011-06-22 | 中国石油天然气股份有限公司 | Heavy aromatic hydrocarbon lightening catalyst and preparation method and application thereof |
| CN101734986A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Method for hydrogenation pyrolysis of prolific benzene and xylene by using pyrolysis gasoline |
| CN104174428A (en) * | 2013-05-22 | 2014-12-03 | 中国石油化工股份有限公司 | Catalyst and method for lightening C9<+> heavy aromatics by use of catalyst |
| CN104174428B (en) * | 2013-05-22 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of catalyst and its method for C9 or more heavy aromatic hydrocarbon light |
| CN108786902A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of heavy aromatics conversion catalyst and preparation method thereof |
| CN108786902B (en) * | 2017-05-02 | 2021-03-05 | 中国石油化工股份有限公司 | Heavy aromatic hydrocarbon conversion catalyst and preparation method thereof |
| CN109395727A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics lightening catalyst |
| CN109395727B (en) * | 2017-08-18 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for conversion of polycyclic aromatic hydrocarbon into light aromatic hydrocarbon |
| CN115193471A (en) * | 2022-05-11 | 2022-10-18 | 中海油天津化工研究设计院有限公司 | Hydrocracking catalyst for distillate oil containing heavy aromatics and application thereof |
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| CN1048425C (en) | 2000-01-19 |
| TW408033B (en) | 2000-10-11 |
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