CN1047962C - Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst - Google Patents
Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst Download PDFInfo
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- CN1047962C CN1047962C CN95116461A CN95116461A CN1047962C CN 1047962 C CN1047962 C CN 1047962C CN 95116461 A CN95116461 A CN 95116461A CN 95116461 A CN95116461 A CN 95116461A CN 1047962 C CN1047962 C CN 1047962C
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Abstract
The present invention relates to a polymetal coated catalyst for alkyl aromatic isomerization. The catalyst is prepared from 0.1 to 0.4 wt% Pt or 0.2 to 0.8 wt% Pd, 0.01 to 0.20 wt% of Re and 0.05 to 0.50 to wt% of Sn; the carrier of the catalyst is prepared from 10 to 60 wt% of zeolite with MOR structure, 0 to 15 wt% of ZSM-5 zeolite and 40 to 80 wt% of aluminum oxide. The catalyst is formed by the method that the zeolite and the aluminum oxide are mixed and formed to obtain the carrier, ammonium ions and sodium ions in the zeolite are exchanged to a certain exchange extent, and the carrier is soaked by active metal. The catalyst has favorable isomerization activity, selectivity and activity stability, and is suitable for preparing contraposition products in the isomerization process of aromatic hydrocarbon of C8, C9 and C10.
Description
The invention relates to a kind of polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof, more particularly, the invention relates to contain in a kind of carrier in zeolite and aluminium oxide, the active component and contain polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst of Pt or Pd noble metal and preparation method thereof.
C
8Aromatic hydrocarbons by to,, the mixture formed of ortho position dimethylbenzene and ethylbenzene, they can obtain from technologies such as catalytic reforming, petroleum cracking.Wherein more to the purposes of, ortho position dimethylbenzene, as can be used as the basic material of polyester and phthalic anhydride.To, ortho position dimethylbenzene can be from C
8Separate obtaining in the mixture of aromatic hydrocarbons, remaining raffinate, can adopt isomerization method be translated into again to,, the equilibrium mixture of ortho position dimethylbenzene, this is a kind of effective means of increasing production paraxylene.
In order to improve C
8The isomerisation conversion of aromatic hydrocarbons and ethylbenzene conversion are the conversion ratio of dimethylbenzene, developed multiple isomerization process method abroad, as OCTAFINING method (EngeIhand company), ISOMAR method (Uop Inc.), ISOENE-II method (toray company) etc., what all adopt in these processes is difunctional noble metal catalyst, this is at USP3,637,881, USP3,767,721, DE2, disclosure is all arranged in 823,567, and the most general isomerized commercial catalyst (product of EMC and Uop Inc.) that is used for also all is difunctional noble metal catalysts at present.The composition of these catalyst all is that Pt and/or Pd load on h-mordenite-alumina support, its preparation method roughly is: earlier the sodium type modenite of powdery is carried out ion-exchange with ammonium salt solution or watery hydrochloric acid and remove wherein part sodium ion, the h-mordenite that necessarily takes off the sodium degree is made in drying, roasting, again with load aluminium oxide and the binding agent of precious metals pt or Pd mix, moulding makes catalyst.This preparation method's yield is lower, and energy consumption is higher.
EP458 discloses a kind of C of being used in 378
8The carbon monoxide-olefin polymeric of aromatics isomerization, it is active component with Pt, to contain 2～3% alkali-metal modenites that are exchanged for Hydrogen and to be selected from boehmite or γ-Al
2O
3Binding agent be carrier.Its preparation method is: earlier modenite being exchanged into Hydrogen mixes with binding agent then, or modenite earlier and binding agent mixed-forming and then be exchanged into Hydrogen, supporting Pt, roasting, reduction more at last.
Also disclose among the applicant's the CN 89100145X a kind of with hydrogen sodium type modenite and aluminium oxide be carrier-supported precious metal, be used for C
8The catalyst of Alleyl aromatics isomerizating.
Since the ZSM series zeolite was come out, people had developed the isomerization catalyst that much contains this zeolite again, as: contain ZSM-5 zeolite (USP4,100,262); Contain ZSM-25 zeolite (EP15702); Contain ZSM-39 zeolite (USP4,357,233); Contain mesomorphic phase zeolite (EP18,090 among the ZSM5/ZSM11; EP65,401); Silicon-aluminum containing than greater than 12, restricted index is zeolite (USP4,428,819) of 1～12 or the like.
USP4 relates to a kind of catalyst that is used for Alleyl aromatics isomerizating in 694,114, and this catalyst is a carrier with ZSM-23 and aluminium oxide, and load hydrogenation or dehydrogenation metal are as Pt, Pd, Ni etc.
EP390, disclosed in 058 then is that ZSM type zeolite and aluminium oxide with silica alumina ratio 30～200 is carrier, supporting Pt-Sn and/or In are that catalyst is used for C
8The isomerization of aromatic hydrocarbons.
At USP 4,467, also relate to a kind of C that is used for that contains two zeolites in 129
8The catalyst of Alleyl aromatics isomerizating, this catalyst is by acid type modenite and specific acid type zeolite, forms carrier as ZSM-5 ,-8 ,-11 etc., also can contain other component, as the inertia aluminium oxide, load has the metallic element that is selected from one of Re, Mo, W, V on this carrier.The roughly preparation method of this catalyst is: two zeolites and diluent (as aluminium oxide) are mixed, add binding agent (as aluminium colloidal sol), mix pinch, dry, roasting behind the extruded moulding, article shaped exchanged to ammonium salt solution necessarily takes off roasting, final impregnating metal component and activation behind the sodium degree.
Purpose of the present invention is exactly to provide a kind of alkylaromatic hydrocarbon is had the catalyst of excellent isomerization performance on the basis of above-mentioned prior art, make isomerization process can access alkylaromatic hydrocarbon to,, the equilibrium mixture at ortho position.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
Other purpose of the present invention can be learnt from the specification that comprises embodiment.
Activity of such catalysts component provided by the invention is 0.1～0.4 heavy %Pt or 0.2～0.8 heavy %Pd, 0.01～0.20 heavy %Re and 0.05～0.50 heavy %Sn; Its carrier is 10～60 heavy %MOR structural zeolites, 0～15 heavy %ZSM-5 zeolite and 40～80 heavy % aluminium oxide.This Preparation of catalysts method is: carrier is made in the moulding of mixture elder generation, the roasting of na-pretreated zeolite and aluminium oxide or its precursor, with ammonium salt solution the sodium exchange degree that it exchanges until zeolite is reached 30～95%, dried carrier floods with the compound solution of each activity component metal, then activation.
According to catalyst provided by the invention, the active component of its load is three kinds of metallic element: Pt or Pd, Re and Sn, and its content (is benchmark with the catalyst weight) separately is: 0.1～0.4 heavy %Pt or 0.2～0.8 heavy %Pd, 0.01～0.20 heavy %Re and 0.05～0.50 heavy %Sn.The carrier of this catalyst is the complex carrier that zeolite and aluminium oxide are formed, zeolite in this complex carrier can be the zeolite of the single a kind of MOR of having structure, the also two zeolites that can form by the zeolite and the ZSM-5 zeolite of this MOR of having structure, its content (is benchmark with the vehicle weight) separately is: the zeolite with MOR structure of 10～60 heavy %, the aluminium oxide of the ZSM-5 zeolite of 0～15 heavy % and 40～80 heavy %.Table 1
D value (A) I/I
0
13.74±0.10 W-VW
9.13±0.10 M-W
6.60±0.10 W
6.40±0.06 W-VW
5.81±0.03 VW
4.53±0.03 W
3.99±0.03 S
3.75±0.03 VW
3.47±0.03 VS
Intensity in the table: VS80～100%; S60～80%; M40～60%; W20～40%;
VW＜20％。
The zeolite of the wherein said MOR of having structure has the X-ray diffraction data shown in the table 1, and its anhydrous chemical composition (in oxide mol ratio) expression formula is: 1.0～7.0Na
2OAl
2O
310～60SiO
2, it to the absorption weight ratio of n-hexane and cyclohexane less than 1.0.Employed this zeolite in catalyst provided by the present invention, its silica alumina ratio should be advisable with 10～30, and its crystallite dimension should be to be advisable less than 1 micron.This zeolite is to be raw material with amorphous aluminum silicide microballoon, NaOH and water, with sodium chloride or sodium chloride-triethanolamine is that template agent crystallization makes, and Chinese patent application number is the detailed content that has disclosed this zeolite and synthetic method thereof in 951164562 the application for a patent for invention.
The invention provides employed ZSM-5 zeolite in the catalyst, its silica alumina ratio should be advisable with 100～500, and its crystallite dimension should be to be advisable less than 1 micron.
Used aluminium oxide can be η-Al in the complex carrier
2O
3, also can be γ-Al
2O
3, but γ-Al preferably
2O
3, the high-purity γ-Al that makes by the low-carbon alkoxy aluminium hydrolysis especially
2O
3This high-purity γ-Al
2O
3The preparation method be disclosed among the CN85100218.8.
According to above-mentioned Preparation of catalysts method provided by the invention, this catalyst can make by following four steps:
1. the preparation of carrier: carrier is made in the moulding of mixture elder generation, the roasting of na-pretreated zeolite and aluminium oxide or its precursor, specifically, promptly be that the mixed zeolite of the zeolite with MOR structure of sodium type or this zeolite and ZSM-5 zeolite and aluminium oxide or its corresponding precursor hydrated alumina are mixed according to predetermined ratio, can add in the mixed powder rare nitric acid as peptizing agent in order to moulding.The concentration of rare nitric acid is generally 1～5 heavy %, is preferably 1.5～3.0 heavy %.With 1: 0.25～0.60, best 1: 0.35～0.45 is advisable the addition of rare nitric acid with the weight ratio of powder and acid solution.The powder that adds acid solution through mixedly pinch, after the moulding, drying, in air atmosphere 470～650 ℃, best 500～600 ℃ of roastings 2～8 hours, best 3～6 hours.
2. the ammonium of carrier exchange: the sodium exchange degree that carrier exchanges until zeolite is reached 30～95% with ammonium salt solution.Specifically, promptly be in room temperature to 120 ℃ with the above-mentioned carrier that makes, best 85～100 ℃ are descended with 0.1～0.8N, the ammonium salt solution that is selected from ammonium chloride, ammonium nitrate, ammonium sulfate of best 0.2～0.5N carries out the ion-exchange several times to it, exchanges 1～6 hour at every turn, best 1～3 hour, sodium exchange degree until zeolite reaches 3095%, preferably reach 55～85%, filter then, the flush away Na that dissociates
+
3. the dipping of active component: dried carrier floods with the compound solution of each activity component metal.Specifically, promptly be with the carrier after the ammonium exchange in room temperature, liquid-solid ratio be under 1～3 the condition with the compound solution dipping of Pt or Pd, Re and Sn 8～60 hours, best 12～36 hours, filter then, drying.The compound of said each metal is meant the soluble compound that is generally used for flooding, as chloroplatinic acid, palladium bichloride, perrhenic acid, solubility pink salt (as SnCl
2Deng).Pink salt wherein also can be introduced in advance in the aluminium oxide and mix with zeolite.
4. the activation of catalyst: this activation process is in air atmosphere 400～600 ℃, best 450～550 ℃ 1～10 hour down, finished in best 3～6 hours.
Compared with prior art, catalyst provided by the invention is owing to selected the particular zeolite with MOR structure for use, determined the complex carrier of specific composition, and many metals of specific composition have been mated, thereby its isomerization activity, selectivity and activity stability all reach higher level, and make isomerization process can obtain alkylaromatic hydrocarbon to,, the equilibrium mixture at ortho position.This catalyst is applicable to that not only the ethyl-benzene level scope is the C of 10～40 heavy %
8Aromatics isomerization, but also can be used for C
9And C
10The aromatics isomerization process produce the contraposition product.
This method for preparing catalyst provided by the invention not only can guarantee giving full play to of each active component function in the catalyst, make the cooperative effect between active component and the carrier reach best, and the loss of zeolite when having reduced dust that support material brings and ion-exchange significantly, improved the yield of zeolite and the exchange efficiency of ammonium salt.
Following example will give further instruction to the present invention, but not thereby limiting the invention.
The zeolite with MOR structure used in the example is synthetic according to disclosed method among the CN951164562; ZSM-5 zeolite and γ-Al
2O
3Be industrial products.
Symbol description related in the example is as follows:＜C
7 N+P-7 cycloalkane and alkane that carbon atom is following; C
8 N+PThe cycloalkane of-8 carbon atoms and alkane; B-benzene; T-toluene; EB-ethylbenzene; The PX-paraxylene; The MX-meta-xylene; The OX-ortho-xylene.
PX/ ∑ X, C in the example
8The computational methods of hydrocarbon yield and EB conversion ratio are as follows:
PX, MX and OX concentration sum * 100% in the concentration ÷ product of PX in the PX/ ∑ X=product
C
8∑ C in hydrocarbon yield=product
8Concentration ÷ raw material in ∑ C
8Concentration * 100%, ∑ C wherein
8Concentration be PX, MX, OX, EB and C
8Non-aromatics concentration sum.
EB concentration * 100% in the difference ÷ raw material of EB concentration in EB conversion ratio=raw material and the product
Comparative Examples 1
Pt-Re/ modenite-γ Al
2O
3The preparation of comparative sample.
With 25 gram silica alumina ratios is 12.5 modenite (in butt) and 75 gram γ-Al
2O
3Mix, the nitric acid that adds 40 milliliter of 2 weight % mixes to be pinched, and 110～120 ℃ of dryings are 1 hour behind the extruded moulding, and 550 ℃ of roastings promptly got carrier in 4 hours in the air atmosphere.
Get 10 the gram carriers, with 25 milliliter 2 the weight % NH
4Cl solution is 90 ± 10 ℃ of following ion-exchanges 2 hours, the Na that flush away is free
+, drying.Can calculate its sodium exchange degree by the sodium content in the forward and backward zeolite of ion-exchange is 75%.
Flood carrier after the exchange of above-mentioned ammonium with chloroplatinic acid and perrhenic acid, make the Pt of its load 0.4 heavy % and the Re of 0.1 heavy %, the activation 4 hours in 500 ℃ of air of dry back.
This comparative catalyst's note is made sample A.
Comparative Examples 2
Pt-Sn/ modenite-γ Al
2O
3The preparation of comparative sample.
Preparation condition is identical with Comparative Examples 1 with the preparation method, load that different is on the carrier be the Pt of 0.4 heavy % and the Sn of 0.2 heavy %.
This comparative catalyst's note is made sample B.
Example 1
The invention provides Preparation of catalysts
Get silica alumina ratio and be 12.3 the zeolite with MOR structure, silica alumina ratio and be 150 ZSM-5 zeolite, make various different catalyst sample C, D, E, F, G, H, I and the J that form according to the method described in the Comparative Examples 1.The sample composition of all these catalyst samples and Comparative Examples 1 and 2 is all listed in table 2.
Table 2
*Silica alumina ratio is 20;
*Silica alumina ratio is 300;
*The tin component is immersed in γ-Al in advance
2O
3On.
Example 2
This example illustrates that catalyst provided by the invention has good dimethylbenzene isomery performance.
To the sample A and the B of above-mentioned comparative example 1 and 2, and catalyst sample C～J provided by the invention carries out C on 10 milliliters small-sized reaction unit
8The aromatics isomerization reactivity is estimated.Be reflected at 380 ℃, when 0.8 MPa pressure, weight space velocity 4.0
-1, carry out under 1000: 1 the condition of hydrogen to oil volume ratio, hydrogen once passes through, the catalyst sample loading amount is 5 grams.Used raw material is formed (heavy %):＜C
7 N+P: 0.16; C
8 N+P: 6.45; B:0.53; T:0.65; EB:12.24; PX:0.0; MX:53.70; OX:26.28.Evaluation result is listed in table 3 (heavy %).
Table 3
Sample P X concentration PX/ ∑ X C
8Hydrocarbon yield EB conversion ratio
A 17.5 22.0 96.5 20.0
B 17.0 21.5 96.8 25.0
C 18.2 22.7 97.5 27.0
D 18.3 22.8 97.4 23.5
E 18.7 23.1 97.8 30.0
F 18.7 22.9 97.7 25.4
G 19.0 23.3 98.0 25.1
H 18.2 22.9 97.2 35.6
I 17.0 22.1 96.7 33.4
J 18.4 22.7 98.0 24.5
Example 3
This example illustrates that catalyst provided by the invention is applicable to the isomerization of different technology conditions.
With the invention provides catalyst sample E, under the condition of reaction unit, catalyst loading amount and the raw material identical, carry out the test of different technology conditions with example 2.Hydrogen is once to pass through equally.Its result of the test is listed in table 4.
Table 4
| During process conditions temperature weight space velocity hydrogen-oil ratio pressure ℃ -1(volume) MPa | Reaction result, heavy % PX concentration PX/ ∑ X C 8Hydrocarbon EB yield conversion ratio |
| 390 4.0 1000/1 0.6 390 4.0 1000/1 1.8 440 4.0 1000/1 0.8 380 2.5 1000/1 0.6 380 4.0 1000/1 0.8 400 10.0 1000/1 0.9 380 4.0 1500/1 0.7 380 4.0 700/1 0.7 | 17.0 21.9 98.4 13.0 18.2 22.0 96.5 30.0 18.5 23.1 94.8 27.0 19.1 23.2 96.3 17.5 18.9 23.1 98.3 18.0 16.2 21.0 98.5 12.2 18.0 23.0 97.9 15.0 18.3 23.0 97.6 17.0 |
Example 4
Example 4
This example illustrates that catalyst provided by the invention is applicable to the C of different ethyl-benzene level
8The aromatics isomerization process.
With catalyst sample E provided by the invention, under the condition of the reaction unit identical, operating condition, catalyst loading amount with example 2 respectively to the C of two kinds of inconsiderate ethyl-benzene level (22.62 heavy % and 11.25 heavy %)
8Raw material carries out aromatics isomerization.Reaction result is listed in table 5.
Table 5
| Raw material is formed, and heavy % product is formed, heavy % I II I II | |
| ＜C 7 N+P C 8 N+P B T EB PX MX OX C 8Hydrocarbon PX/ ∑ X C 8Hydrocarbon yield EB conversion ratio | 0.028 0.036 10.30 12.62 0.34 0 45 1.20 1.38 22.62 11.25 15.58 8.96 2.44 2.89 42.67 48.87 20.40 22.51 98.43 98 13 22.01 22.28 96.96 97.04 31.11 21.40 |
Example 5
The explanation of this example the invention provides catalyst and has good isomerization activity stability.
On 30 milliliters medium-sized reaction unit, be that 1000: 1, pressure are under the condition of 0.8～0.9 MPa at 380～383 ℃, weight space velocity 4 time-1, hydrogen to oil volume ratio, adopt the C identical with example 2
8Raw material carries out the activity stability test with catalyst sample E, and the catalyst loading amount is 22 milliliters.Product when reacting the 1000th hour (heavy %) composed as follows: C
8 N+P: 8.15; B:0.33; T:0.96; EB:9.80; PX:18.36; MX:42.05; OX:18.36; PX/ ∑ X:23.23; C
8Hydrocarbon yield: 97.80; EB conversion ratio: 19.93.The carbon deposit that turns round on the catalyst sample after 1000 hours only has 0.70 heavy %.
Example 6
The explanation of this example the invention provides catalyst and is equally applicable to C
9Aromatics isomerization.
On 10 milliliters small-sized reaction unit, 430 ℃, when 0.8 MPa, liquid hourly space velocity (LHSV) 3.1
-1Hydrogen to oil volume ratio is under 1000: 1 the condition, with catalyst sample E the trimethylbenzene raw material is carried out the isomerization reaction test, and reaction result is listed in table 6.
Table 6
| Raw material is formed, heavy % | Product is formed, heavy % | |
| Other C of total xylene mesitylene pseudocumene 1,2,3-trimethylbenzene 9The aromatic hydrocarbons durene other | 0.03 0.45 99.12 - 0.37 - 0.03 | 6.10 19.69 59.03 8.42 0.21 4.9 1.65 |
Example 7
This example illustrates that catalyst provided by the invention is equally applicable to C
10The isomerization of aromatic hydrocarbons.
On 10 milliliters of small-sized reaction units, 370 ℃, when 0.7 MPa, liquid hourly space velocity (LHSV) 3.0
-1, under 1500: 1 the condition of hydrogen to oil volume ratio, carry out the isomerization reaction test with catalyst sample E p-Diethylbenzene raw material, reaction result is listed in table 7.
Table 7
| Raw material is formed, heavy % | Product is formed, heavy % | |
| Non-aromatics C 8～C 10Aromatic hydrocarbons *Adjacent diethylbenzene＞the C of NSC 62102 p-Diethylbenzene 10The total diethylbenzene p-Diethylbenzene of aromatic hydrocarbons/total diethylbenzene diethylbenzene conversion ratio | 0.03 6.16 79.82 9.20 3.97 0.82 92.99 | 8.91 6.63 50.42 21.30 6.16 6.58 77.88 27.35 83.74 |
*C herein
10Aromatic hydrocarbons does not comprise diethylbenzene.
Claims (10)
1. catalyst that contains zeolite-alumina support supported V III family noble metal, it is characterized in that this activity of such catalysts component is 0.1～0.4 heavy %Pt or 0.2～0.8 heavy %Pd, 0.01～0.20 heavy %Re and 0.05～0.50 heavy %Sn, carrier is 10～60 heavy %MOR structural zeolites, 0～15 heavy %ZSM-5 zeolite and 40～80 heavy % aluminium oxide.
2. according to the described catalyst of claim 1, it is characterized in that said MOR structural zeolite has the X-ray diffraction data shown in the following table, its anhydrous chemical composition expression formula in oxide mol ratio is: 1.0～7.0Na
2OAl
2O
310～60SiO
2, it to the absorption weight ratio of n-hexane and cyclohexane less than 1.0.
D value (A) I/I
0
13.74±0.10 W-VW
9.13±0.10 M-W
6.60±0.10 W
6.40±0.06 W-VW
5.81±0.03 VW
4.53±0.03 W
3.99±0.03 S
3.75±0.03 VW
3.47±0.03 VS
Intensity in the table: VS80～100%; S60～80%; M40～60%; W20～40%; VW＜20%.
3. according to the described catalyst of claim 2, the silica alumina ratio that it is characterized in that said MOR structural zeolite is 10～30, and crystal grain is less than 1 micron.
4. according to the described catalyst of claim 1, the silica alumina ratio that it is characterized in that said ZSM-5 zeolite is 100～500, and crystal grain is less than 1 micron.
5. according to the described catalyst of claim 1, it is characterized in that said aluminium oxide is η-Al
2O
3Or Y-Al
2O
3
6. claim 1 Preparation of catalysts method, it is characterized in that carrier is made in the moulding of mixture elder generation, the roasting of na-pretreated zeolite and aluminium oxide or its precursor, with ammonium salt solution the sodium exchange degree that it exchanges until zeolite is reached 30～95%, dried carrier floods with the compound solution of each activity component metal, then activation.
7. in accordance with the method for claim 6, it is characterized in that said carrier be mixture with the mixed zeolite of sodium type MOR structural zeolite or this zeolite and ZSM-5 and aluminium oxide or its precursor mix pinch, moulding, 470～650 ℃ of roastings in air of dry back made in 2～8 hours.
8. in accordance with the method for claim 6, it is characterized in that said ion-exchange is under room temperature to 120 ℃, finished in 1～6 hour with the each exchange of the ammonium salt solution of 0.1～0.8N.
9. in accordance with the method for claim 6, it is characterized in that said dipping is is to flood 8～60 hours under 1～3 the condition in room temperature, liquid-solid ratio with chloroplatinic acid or palladium bichloride, perrhenic acid, tin-salt solution.
10. in accordance with the method for claim 6, it is characterized in that said activation in air 400～600 ℃ finished in 1～10 hour down.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116461A CN1047962C (en) | 1995-10-06 | 1995-10-06 | Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst |
| US08/597,161 US5759950A (en) | 1995-06-10 | 1996-02-06 | Catalyst supported with noble metal(s) for the isomerization of alkylaromatics |
| KR1019960004594A KR100303457B1 (en) | 1995-10-06 | 1996-02-26 | A catalyst comprising a supported noble metal for alkyl aromatic hydrocarbon isomerization |
| RU96103680A RU2137542C1 (en) | 1995-10-06 | 1996-02-29 | Catalyst containing precious metal on carrier for isomerization of alkylaromatic compounds (versions) and method of preparation thereof |
| DE19641149A DE19641149A1 (en) | 1995-10-06 | 1996-10-07 | Catalysts for isomerisation of alkyl-aromatics |
| TW085113902A TW396057B (en) | 1995-10-06 | 1996-11-13 | Catalys supported with noble metal(s) for the isomerization of alkylaromatics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95116461A CN1047962C (en) | 1995-10-06 | 1995-10-06 | Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1149000A CN1149000A (en) | 1997-05-07 |
| CN1047962C true CN1047962C (en) | 2000-01-05 |
Family
ID=5080874
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|---|---|---|---|
| CN95116461A Expired - Lifetime CN1047962C (en) | 1995-06-10 | 1995-10-06 | Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst |
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| CN (1) | CN1047962C (en) |
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| CN101380590B (en) * | 2008-07-13 | 2011-07-20 | 中国石油兰州石油化工公司 | Selective hydrogenation catalyst for carbon five fraction and preparation and use thereof |
| CN103769206B (en) * | 2012-10-25 | 2017-07-14 | 中国石油化工股份有限公司 | EUO structural molecule sieve catalysts and preparation method thereof |
| CN106745050A (en) * | 2016-11-17 | 2017-05-31 | 中国科学院生态环境研究中心 | A kind of molecular sieves of noble metal support type ZSM 5 and its preparation method and application |
| CN107990580B (en) * | 2017-11-07 | 2019-05-10 | 西安交通大学 | A kind of the self-cascade heat pump system and operational mode of separating for several times injection synergy |
| CN115722259B (en) * | 2021-08-26 | 2024-02-09 | 中国科学院广州能源研究所 | Synthesis method of space adjacent bimetallic heteroatom molecular sieve |
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| US4467129A (en) * | 1982-11-24 | 1984-08-21 | Toray Industries, Inc. | Conversion of xylenes containing ethylbenzene |
| CN1044053A (en) * | 1989-01-13 | 1990-07-25 | 中国石油化工总公司石油化工科学研究院 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation method thereof |
| EP0390058A1 (en) * | 1989-03-29 | 1990-10-03 | Teijin Limited | Catalyst composition, process for cracking non-aromatic hydrocarbons and process for isomerizing C8 aromatic hydrocarbons |
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| CN1149000A (en) | 1997-05-07 |
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