CN1162502A - Catalyst comprising zeolite of structure type mazzite and its use for dismutation and/or transalkylation of alkylaromatic hydrocarbons - Google Patents
Catalyst comprising zeolite of structure type mazzite and its use for dismutation and/or transalkylation of alkylaromatic hydrocarbons Download PDFInfo
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- CN1162502A CN1162502A CN 97101278 CN97101278A CN1162502A CN 1162502 A CN1162502 A CN 1162502A CN 97101278 CN97101278 CN 97101278 CN 97101278 A CN97101278 A CN 97101278A CN 1162502 A CN1162502 A CN 1162502A
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Abstract
A zeolite of mazzite structure comprising silicon and at least one element T(where T is selected from Ga or Al, optimal is Al), and in which the global Si/T atomic ratio is 5-100 and the number of extra-lattice T atoms is less than 15% of the total T atoms in the zeolite. Also claimed, is the preparation of the zeolite from a crude synthetic product and its use in dismutation reactions, and its preparation by extraction of element T from the zeolitic framework, preferably by dealuminization of the framework by means of at least one hydrothermal treatment followed by at least one acid attack. The invention relates to said zeolite, at least a part of which takes on acid modality, or at least one of it is selected from the periodic table group IB and group VIII, and at least one matrix catalyst. The uses of said catalyst for the dismutation of alkylaromatic hydrocarbons, and preferably for the dismutation of toluene to produce benzene and xylenes, and/or for the transalkylation of alkylaromatic hydrocarbons, preferably for the transalkylation of toluene and trimethylbenzenes to produce xylenes are also disclosed.
Description
The present invention relates to a kind of silicon and at least a element T that is selected from the group of forming by gallium and aluminium of containing, the zeolite of the mazzite structure type of aluminium preferably, wherein the outer T atomicity of grid is lower than about 15% of the T total atom number that exists in this zeolite, its total Si/T atomic ratio is 5-100, and at least hydrothermal treatment consists of employing, follow the chemical action of at least one hypo acid, element T prepares its zeolite in the zeolite framework (or grid) by extracting, and preferably prepares its zeolite by the framework dealumination effect.The invention still further relates to a kind of catalyzer, this catalyzer contains the described zeolite that is sour form to small part, perhaps at least aly be selected from element and at least a matrix in the group of forming by I family in the period of element sorted table and group VIII, and the application of described catalyzer in the alkylaromatic hydrocarbon disproportionation, preferably toluene disproportionation generates benzene and dimethylbenzene, and/or the application in the transalkylation of alkylaromatic hydrocarbon, preferably the transalkylation of toluene and trimethylbenzene generates dimethylbenzene.
Having described many in the prior art is the disproportionation of main component and the catalyzer of transalkylation with the mordenite.The mordenite that uses has one dimension micropore grid, and the diameter in its hole is 7 * 6.5 dusts (1 dust=1.10
-10Rice) (" Atlas of Zeolite StructureTypes ", W.M.Meier et D.H.Olson, the 3rd edition, 1992).US3506731 patent and french patent application FR-A-2367533 are so, have used the mordenite that is hydrogen form in this part United States Patent (USP).US3281483 patent or US3780121 also are like this, wherein the former has mentioned mordenite main and silver ions or nickel ion exchange, the latter has mentioned the mordenite that is sorted in I B-group metal exchange in the table with period of element, this zeolite is characterised in that the Si/Al atomic ratio is 6-40, perhaps the US3629351 patent is that so this patent also relates to a kind of mordenite that contains IB family, VA family, VIA family, IIA family and group VIII metal ion in the period of element sorted table equally.
Recently, the US5210356 patent is claimed through the dealuminization modification, also the application of the toluene disproportionation catalyst of the omega zeolite of nickel-loaded.
On the other hand, the US5371311 patent has illustrated a kind of catalyzer that contains omega zeolite to us, this zeolite is with alkali metal cation with as the organic reagent synthetic of organic structuring agent, then by calcining under air, ion-exchange, calcining in the presence of water vapor, handle with the low pH ammonium ion aqueous solution at last and carry out modification, like this, its catalyzer obtains good physical-chemical property, with in the conversion reaction of hydrocarbon, specifically be good catalytic performance in the disproportionation of alkylaromatic hydrocarbon and transalkylation.
In surprise, a kind of to small part, the zeolite that preferably virtually completely is the mazzite structure type of sour form, this zeolite contains the outer T atomicity of grid and is lower than and has 15% of T total atom number in the described zeolite, when being added to this zeolite in a kind of catalyzer, compare with the catalyzer of prior art, can obtain catalytic performance, the especially selectivity of the transalkylation reaction (as toluene and trimethylbenzene) of good alkylaromatic hydrocarbon (as toluene) disproportionation reaction and/or alkylaromatic hydrocarbon.
The present invention relates to a kind of zeolite of mazzite structure type, omega zeolite preferably, this zeolite contains silicon and at least a element T that is selected from the group of being made up of gallium and aluminium, be preferably aluminium, its Si/T total atom ratio is 5-100, preferably 6-80,8-60 more preferably, the Si/T ratio of skeleton is like this, and the outer T atomicity of grid is lower than 15% of the T total atom number (being T atomicity sum in outer T atomicity of grid and the lattice framework) that contains in the described zeolite, preferably is lower than 10%.
The invention still further relates to a kind of catalyzer, this catalyzer contains and a kind ofly is sour form to small part, the zeolite that preferably virtually completely is the mazzite structure type of sour form, this zeolite contains silicon and at least a element T that is selected from the group that gallium and aluminium forms, be preferably aluminium, its Si/T total atom ratio is 5-100,6-80 preferably, 8-60 more preferably, the Si/T ratio of skeleton is like this, the outer T atomicity of grid is lower than 15% of the T total atom number that contains in the described zeolite, preferably be lower than 10% and perhaps at least a element and at least a matrix (being tackiness agent) that is selected from the group of forming by IB family and group VIII in the period of element sorted table.
Described matrix generally is selected from the composition in the group of being made up of clay (for example natural clay of kaolin or wilkinite and so on), magnesium oxide, aluminum oxide, silicon-dioxide, titanium oxide, boron oxide compound, zirconium dioxide, aluminum phosphate, titanium phosphate, zirconium phosphate and silica-alumina, preferably is selected from the composition in the group of being made up of aluminum oxide and clay.
The zeolite of mazzite structure type of the present invention generally is selected from the group of being made up of omega zeolite, mazzite, LZ-202 zeolite, gallosilicate mazzite or ZSM-4 zeolite, omega zeolite preferably, its main bore dia is about 7.4 dusts, has one dimension micropore grid (" Atlas ofZeolite Structure Types ", W.M.Meier et D.H.Olson, the 3rd edition, 1992).
When catalyzer of the present invention contained this zeolite, the zeolite of mazzite structure type was to small part, preferably virtually completely was sour form, promptly was hydrogen form (H
+), the sodium content of this zeolite generally is lower than 0.6% (weight), preferably is lower than 0.1% (weight).
Catalyzer of the present invention generally contains 10-99%, and preferably 20-95% is the zeolite of the mazzite structure type of sour form to small part.Catalyzer of the present invention contain at least a be selected from by the period of element sorted table under the situation of element in the group formed of IB family and group VIII, described weight content this or these elements generally is 0.01-10%, preferably 0.05-7%, more preferably 0.10-5%.Add to that 100% (weight) generally is made up of the matrix of this catalyzer.
The invention still further relates to described mazzite structure type zeolite and described Preparation of catalysts method.
In order to prepare the zeolite of mazzite structure type of the present invention, at T is under the preferable case of Al, adopt any method well known by persons skilled in the art, zeolite to rough synthetic mazzite structure type carries out dealuminzation, when T is aluminium, carry out described dealuminzation particularly, promptly flow down and carry out calcining step at dry air according to the operating method of describing in the US4780436 patent, its purpose is to remove the organic structuring agent of sorption in this zeolite micropore crack, uses at least a NH
4NO
3Solution carries out primary ions exchange at least, so that in fact remove any alkali metal cation that exists at this zeolite cation position, especially sodium, carry out the circulation of at least one framework dealumination then, this circulation comprises at least once in the presence of water vapor, generally is the chemical action that at least one hypo acid is followed in the calcining carried out under 550-850 ℃ the condition in temperature.But change the calcination condition (temperature, water vapor pressure and treatment time) in the presence of water vapour, and the chemical action condition of the calcining back acid ratio of zeolite quality (chemical action time, the concentration of using acid and the sour volume with), so that make the outer Al atomicity of residual grid be lower than 15% of total Al atomicity in the described zeolite.
At T is under the preferable case of Al, this framework dealumination circulation comprises the acidifying action step of at least one calcining step under water vapor and at least one mazzite structure type zeolite in acid medium, and this circulation can repeat to this dealuminzation mazzite structure type zeolite and have the necessary number of times of institute's characteristic that requires.Similarly, under water vapor, after the calcination processing, can carry out repeatedly acidifying effect in succession with the acid solution of different concns.
At T is under the preferred situation of Al, and the aluminium atomicity in the zeolite framework of mazzite structure type can be changed angle rotation with peak value and then be removed to revolve (rotation a l ' angle magique suivi d ' unedeconvolution des pias)
29Si nuclear solid-state nuclear magnetic resonance is measured, perhaps use infrared spectroscopic determination,, can determine Si/Al ratio in skeleton or the grid by constituting the vibrational frequency of element in the stylus point zeolite structure type zeolite framework, therefore, can determine the aluminium atomicity that exists in its grid.When T was aluminium, the shuttle belt of measuring was at tetrahedron T ' O
4Interior asymmetric valence vibrations band, T ' or Siliciumatom, or aluminium atom (1010cm
-1And 1100cm
-1), tetrahedron T ' O
4Outer shuttle belt is 610-660cm
-1
Prepare this catalyzer according to any method well known by persons skilled in the art.Usually, this matrix is mixed with described zeolite, then moulding and can prepare this catalyzer.Possible element in the group of being made up of period of element sorted table IB family and group VIII perhaps can be before moulding, or when mixing, or add toward this zeolite before mixing this zeolite, perhaps preferably after moulding, add.Usually, be to calcine under 250-600 ℃ then after the moulding at typical temperature.Possible element in the group of being made up of period of element sorted table IB family and group VIII can add in described calcining back.In all cases, the general sedimentary selection of described element is, perhaps preferably virtually completely be deposited on this zeolite, perhaps virtually completely be deposited on this matrix, perhaps part is deposited on this zeolite and partly and is deposited on this matrix, these parameters of using when adopting described the deposition are carried out this selection in the manner known to persons skilled in the art, for example select predecessor's character so that carry out described deposition.
IB family and group VIII element preferably are selected from the element in the group of being made up of Ag, Ni and Pt, and more preferably Ni perhaps can also adopt any method well known by persons skilled in the art, is deposited on the zeolite-substrate mixture of moulding in advance.A kind of like this deposition generally is to adopt dried dipping technique, one or more ion exchange techniques or chemical coprecipitation technique to carry out.Under the situation of the ion-exchange of setting out by the predecessor who with silver, nickel or platinum is main component, use as the silver salt of silver chloride or Silver Nitrate and so on, the tetramine title complex of platinum usually, or as the nickel salt of nickelous chloride, nickelous nitrate, nickelous acetate or nickel formate and so on.Can also use this cationic exchange technology, its metal with this metal directly is deposited on the zeolite powder before matrix may mix.
Under the situation of the catalyzer that contains multiple metal, these metals can perhaps fully in an identical manner, perhaps adopt different technology to add before moulding or after the moulding in any order.In the technology of using is under the situation of ion exchange technique, for the metallographic phase that the adds requirement capable repeatedly exchange of going on may be necessary.
For example, wherein a kind of preferred method of preparation catalyzer of the present invention is, reach excellent homogeneity time necessary (for example in ten minutes) lining at the slurry that so obtains, this zeolite is mixed in the wet matrix gel (generally mix and obtain) of aluminum oxide and so on for example by at least a acid and a kind of matrix powder, allow described slurry by generating the extrusion die of extrudate then, for example diameter is the extrusion die of 0.4-4 millimeter.Then, in 100 ℃ of baking ovens, behind the dry several minutes and for example after 2 hours calcining of 400 ℃ of calcinings, for example can adopt the possible metal of ion-exchange deposition as nickel and so on, after the described deposition, carry out last calcining, for example calcine 2 hours at 400 ℃.
Shaping of catalyst of the present invention generally is such, and this catalyzer preferably is tablet, aggregate, extrudate or ball shape, so that its use.
General adopt calcining, usually temperature 250-600 ℃ down described last calcining finish its Preparation of catalysts, preferably, before calcining, carry out drying, for example be generally room temperature to 250 ℃ in temperature, preferably carry out drying in the baking oven under 40-200 ℃.Preferably, described drying step proceeds to its temperature and is raised to and carries out the necessary temperature of described calcining.
After IB family and group VIII element (or multiple element) may deposit, generally at 300-600 ℃, preferably under 350-550 ℃, calcining was 0.5-10 hour in air or oxygen, preferably 1-4 hour.Then,, preferably under 350-550 ℃, in hydrogen, carried out reduction reaction 1-10 hour, preferably 2-5 hour, be basically and have the necessary reduction form of catalytic activity so that obtain described element generally at temperature 300-600 ℃.
The invention still further relates to the application of fast catalyzer in the alkylaromatic hydrocarbon disproportionation, preferably toluene disproportionation generates benzene and dimethylbenzene, and/or the application in the transalkylation of alkylaromatic hydrocarbon, the preferably application of the transalkylation of toluene and general C9+ alkylaromatic hydrocarbon (being that each molecule has at least 9 carbon atoms) is as the transalkylation and/or the disproportionation generation dimethylbenzene of toluene and/or C9+ alkylaromatic hydrocarbon.A kind of like this material of method can contain 0-100%C9+ alkylaromatic hydrocarbon and 0-100% toluene.It is very effective that described catalyzer seems in described application.It is stable especially that composite catalyst of the present invention seems, even contain under the situation of a large amount of heavy aromatics AC9 (+) at pending material also be like this.
These operational conditions are generally as follows: temperature is 250-600 ℃, preferably 330-500 ℃; Pressure is the 10-60 crust, preferably the 20-45 crust; The space velocity of charging is shown with the material kilogram numerical table that every kg catalyst per hour adds, and is 0.1-10, preferably 0.5-4; The mol ratio of hydrogen and hydrocarbon is 2-20, preferably 3-12.
The following examples illustrate the present invention and do not limit its protection domain.
Embodiment 1: the preparation of zeolite 1 of the present invention
The raw material that uses is an omega zeolite, and total Si/Al atomic ratio that this zeolite has is 3.2, and in the weight of dried omega zeolite, the weight content of sodium is about 5.3%, and the volume of structure cell is 2.196nm
3, at-196 ℃ and P/P
oPore volume rate with nitrogen determination under=0.19 condition is that every gram is 0.125 centimetre
3Liquid nitrogen.
This omega zeolite at first carried out described drying and calcining 6 hours in 550 ℃ under air and nitrogen gas stream.Then, the solid that obtains is at about 100 ℃ of 10N NH
4NO
3Carry out the exchange of 3 secondary ions in the solution, each ion-exchange 4 hours.At this moment omega zeolite 625 ℃, 50% water vapor in the presence of carried out hydrothermal treatment consists 4 hours.This zeolite is in about 100 ℃ of chemical actions 4 hours of carrying out acid with 1.5N nitric acid, so that the outer aluminum shot kind of grid that is generated when extracting hydrothermal treatment consists.The volume V (in ml) of the salpeter solution that adds is dry omega zeolite weight P 10 times (V/P=10).
After these were handled, the total Si/Al atomic ratio that is the omega zeolite (Ω 1) of H form was 11.3, used
29The Si/Al ratio is 12 in the skeleton of Si nuclear magnetic resonance measuring, and in dried omega zeolite weight, the weight content of sodium is 160ppm, and the volume of structure cell is 2.145nm
3, at-196 ℃ and P/P
oThe nitrogen loading capacity of measuring under=0.19 condition is 0.214 centimetre
3Liquid nitrogen/gram.
Embodiment 2: the preparation of catalyzer Ω 2 of the present invention
The zeolite omega 1 of embodiment 1 preparation again with the alumina gel extrusion moulding, in order that under dry air, contained the catalyzer Ω 2 of 80% omega zeolite and 20% aluminum oxide after the dry and calcining by weight.
Embodiment 3: the preparation of catalyzer Ω 3 of the present invention
In this embodiment, allow the catalyzer Ω 2 of embodiment 2 preparations and nickelous acetate solution carry out the exchange of 3 secondary ions, so that in this catalyzer, add 1.0% (weight) nickel.
For this reason, catalyzer Ω 2 and 0.5MNi (CH
3CO
2)
2Solution at room temperature stirs contact.Between each ion-exchange, this solid separates with dipping solution, and washs in a large number with exchanged water.It is 0.5 mole every liter to concentration all during each ion-exchange with the concentration re-adjustment of dipping solution.
Wet solid 120 ℃ of dryings 12 hours, flows down in 500 ℃ of calcinings of temperature 1 hour at dry air again.Zhi Bei catalyzer Ω 3 contains the omega zeolite that is hydrogen form, 19.80% aluminum oxide and 0.85% nickel of the outer aluminum shot kind of 79.3% no grid by weight like this.
Embodiment 4: the preparation of non-zeolite omega 4 of the present invention
The raw material that uses be with embodiment 1 in the identical omega zeolite that uses.
Then, at first allow this omega zeolite in air and nitrogen gas stream, carry out described drying and calcining 6 hours in 550 ℃.Allow the solid that obtains at about 100 ℃ of 10N NH again
4NO
3Carry out the exchange of 3 secondary ions in the solution, each ion-exchange 4 hours.At this moment, this omega zeolite carried out hydrothermal treatment consists 4 hours at 625 ℃ in the presence of 50% water vapor.Again with 1N nitric acid in about 100 ℃ of chemical actions 3.5 hours that this zeolite is carried out acid, in order that the outer aluminum shot kind of grid that generates during the extracting section hydrothermal treatment consists.The volume V (in milliliter) of the salpeter solution that adds is dried omega zeolite weight P 10 times (V/P=10).
After these were handled, the total Si/Al atomic ratio that is the omega zeolite (Ω 4) of H form was 6.5, used
29The Si/Al ratio is 12.1 in the skeleton of Si nuclear magnetic resonance measuring, and in dried omega zeolite weight, the weight content of sodium is 155ppm, and the volume of structure cell is 2.147nm
3, at-196 ℃ and P/P
oThe nitrogen loading capacity of measuring under=0.19 condition is 0.195 centimetre
3Liquid nitrogen/gram.
Embodiment 5: the preparation of non-zeolite omega 5 of the present invention
The raw material that uses be with embodiment 1 in the identical omega zeolite that uses.
Yet in this embodiment, this omega zeolite does not carry out dealuminization.At first allow this zeolite in air and nitrogen gas stream, carry out described drying and calcining 6 hours in 550 ℃.Allow the solid that obtains like this at about 100 ℃ of 10N NH then
4NO
3Carry out the exchange of 3 secondary ions in the solution, each ion-exchange 4 hours.At this moment, the ammonium form omega zeolite that makes was so at first calcined 2 hours in the dry air (2 liters of nitrogen of per hour every gram are per hour joined 0.4 liter of dry air of every gram) of nitrogen dilution, only calcined 4 hours in 550 ℃ in dry air stream then.
After these were handled, Zhi Bei the total Si/Al atomic ratio that is H form omega zeolite (Ω 5) was 3.2 like this, used
29The Si/Al ratio is 3.3 in the skeleton of Si nuclear magnetic resonance measuring, and in dried omega zeolite weight, the weight content of sodium is 150ppm, and the volume of structure cell is 2.207nm
3, at-196 ℃ and P/P
oThe nitrogen loading capacity of measuring under=0.19 condition is 0.22 centimetre
3Liquid nitrogen/gram.
Embodiment 6: the preparation of catalyzer C1 and C2 (non-the present invention)
Non-zeolite omega of the present invention 4 and Ω 5 and alumina gel extrusion moulding are in order that help in their operation and the reactor of packing into.Corresponding extrusioning catalyst is designated as C1 and C2, and these catalyzer contain 20% (weight) aluminum oxide.
The catalyzer Ω 2 of embodiment 2 and the catalyzer Ω 3 of embodiment 3, the catalyzer C1 of embodiment 6 and the composition overview of C2 are listed in the table below.
| Catalyzer | Omega zeolite % (weight) | Nickel % (weight) | Aluminum oxide % (weight) |
| Ω 2 of the present invention | ????80.0 | ????0.0 | ????20.0 |
| Ω 3 of the present invention | ????79.32 | ????0.85 | ????19.83 |
| ??C1 | ????80.0 | ????0.0 | ????20.0 |
| ??C2 | ????80.0 | ????0.0 | ????20.0 |
Embodiment 7: the evaluation of all catalyst performances
In fixed-bed reactor, under pressure, use these catalyzer, the material of packing into and constituting in this reactor by pure toluene.
During (benzene+ethylbenzene+dimethylbenzene) productive rate contrast situation of using catalyzer Ω 1 of the present invention and Ω 2 and non-catalyzer C1 of the present invention and C2 to obtain is listed in the table below:
| Catalyzer | Ω (the present invention) | C1 (non-the present invention) | Ω 2 (the present invention) | C2 (non-the present invention) |
| Temperature of reaction (℃) | ????450 | ????450 | ????450 | ????450 |
| Reaction total pressure (crust) | ????30 | ????30 | ????30 | ????30 |
| Productive rate % (weight) (benzene+ethylbenzene+dimethylbenzene) | ????38.0 | ????36.9 | ????38 | ????34.5 |
Catalyzer Ω 1 and Ω 2 comparison shows that with catalyzer C1 and C2's, and (benzene+ethylbenzene+dimethylbenzene) productive rate that catalyzer Ω 1 of the present invention and Ω 2 obtain is higher than the productive rate that all non-catalyzer C1 of the present invention and C2 obtain.
Claims (16)
1, contains silicon and at least a zeolite that is selected from the mazzite structure type of the element T in the group of forming by gallium and aluminium, wherein total Si/T atomic ratio is 5-100, the Si/T ratio of skeleton is like this, and the outer T atomicity of grid is lower than 15% of total T atomicity in the described zeolite.
2, zeolite according to claim 1, as the outer T atomicity of grid be lower than whole as described in the zeolite total T atomicity 10%.
3, according to the described zeolite of arbitrary claim in claim 1 or 2, be aluminium as T.
4, according to the described zeolite of arbitrary claim among the claim 1-3, it is selected from the group of being made up of gallosilicate mazzite, mazzite, LZ-202 zeolite, omega zeolite or ZSM-4 zeolite.
5, according to the described zeolite of arbitrary claim among the claim 1-4.
6, with the zeolite of rough synthetic mazzite structure type, extract the circulation of zeolite framework T element by at least one, the method for preparing the described zeolite of arbitrary claim among the claim 1-5, wherein said circulation comprises at least once calcining in the presence of water vapor, follows the chemical action of at least one hypo acid.
7, preparation method according to claim 6 is the dealuminization of this skeleton as this extraction.
8, a kind of catalyzer, it contain at least a according to arbitrary claim among the claim 1-5 described or according to claim 6 or 7 the preparation, the zeolite of mazzite structure type that is the form of acid to small part, also perhaps contain at least a element and at least a matrix that is selected from the group of forming by IB family and group VIII in the period of element sorted table.
9, catalyzer according to claim 8 virtually completely is sour form as this zeolite.
10, the described catalyzer of arbitrary claim according to Claim 8 or in 9, element as described is selected from the group of being made up of Ag, Pt and Ni.
11, according to Claim 8 the described catalyzer of arbitrary claim-10, described catalyzer contains the 10-99% zeolite, described catalyzer contain at least a be selected from by the period of element sorted table under the situation of element in the group formed of IB family and group VIII, described catalyzer contains the described element of 0.01-10%, and adding to 100% (weight) is to be made of the body portion in this catalyzer.
12, according to Claim 8 the described catalyzer of arbitrary claim-11 is sheet, agent aggregate, extrudate or ball shape.
13,, comprise mixing of this matrix and this zeolite, moulding then, and may the depositing of described element according to the described Preparation of catalysts method of arbitrary claim among the claim 7-12.
14,, be included in temperature 250-600 ℃ of last down calcining according to the described Preparation of catalysts method of claim 13.
15, according to Claim 8 the described catalyzer of arbitrary claim-12, or according to the application in the transalkylation of the disproportionation of alkylaromatic hydrocarbon and/or alkylaromatic hydrocarbon of the catalyzer of arbitrary claim preparation in claim 13 or 14.
16, according to claim 15ly contain the disproportionation of alkylaromatic hydrocarbon of at least 9 carbon atoms and/or the application in the transalkylation at toluene and/or each molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97101278 CN1162502A (en) | 1996-02-09 | 1997-02-09 | Catalyst comprising zeolite of structure type mazzite and its use for dismutation and/or transalkylation of alkylaromatic hydrocarbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9601606 | 1996-02-09 | ||
| CN 97101278 CN1162502A (en) | 1996-02-09 | 1997-02-09 | Catalyst comprising zeolite of structure type mazzite and its use for dismutation and/or transalkylation of alkylaromatic hydrocarbons |
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| Publication Number | Publication Date |
|---|---|
| CN1162502A true CN1162502A (en) | 1997-10-22 |
Family
ID=5165624
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97101278 Pending CN1162502A (en) | 1996-02-09 | 1997-02-09 | Catalyst comprising zeolite of structure type mazzite and its use for dismutation and/or transalkylation of alkylaromatic hydrocarbons |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582799A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Pretreatment method of catalyst for disproportionation and transalkylation of aromatic compounds |
-
1997
- 1997-02-09 CN CN 97101278 patent/CN1162502A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582799A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Pretreatment method of catalyst for disproportionation and transalkylation of aromatic compounds |
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