CN1126603C - Process for preparing selective disproportionation catalyst of toluene - Google Patents
Process for preparing selective disproportionation catalyst of toluene Download PDFInfo
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- CN1126603C CN1126603C CN00119771A CN00119771A CN1126603C CN 1126603 C CN1126603 C CN 1126603C CN 00119771 A CN00119771 A CN 00119771A CN 00119771 A CN00119771 A CN 00119771A CN 1126603 C CN1126603 C CN 1126603C
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- catalyst
- toluene
- molecular sieve
- zsm
- selective disproportionation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for preparing a selective disproportionation catalyst of toluene, which mainly solves the problems of complex procedures and troublesome operation in the process for preparing the selective catalyst in the prior art. The present invention has the technical scheme that firstly, a compound selected from potassium acid phthalate, sodium ethylene diamine tetracetate, sodium sulfosalicylate, potassium tartrate or sodium dodecylbenzene sulfonate is compounded into a solution with the concentration of 10 to 50 wt%, and then, a ZSM-5 molecular sieve modified by metals is added for ion exchange. Thus, the problems are favorably solved. When used for methylbenzene disproportionation, the prepared catalyst has high activity and contraposition selectivity, and the method of the present invention can be applied to industrial production.
Description
The invention belongs to the preparation method of selective disproportionation catalyst of toluene.
Toluene disproportionation process is one of industrial common reaction, and it can change into toluene higher benzene of using value and dimethylbenzene, and wherein the dimethylbenzene product is the thermodynamical equilibrium composition mixture of its three isomers, and the paraxylene that has the call only accounts for 24%.Therefore there is the people to propose the new technology of selective disproportionation, makes reaction system optionally generate paraxylene.Conventional toluene disproportionation catalyst is main active component with modenite, because the modenite channel diameter is bigger, three kinds of isomers of paraxylene do not have the effect of selecting the shape selection.After the beginning of the seventies, ZSM-5 was synthesized, because it is extensively paid attention to alkylation, isomerization, disproportionation, selective cracking process and the catalytic performance that has uniqueness by reactions such as methanol synthesized gasolines.The ZSM-5 zeolite constitutes pore canal system by 10 yuan of oxygen rings, has medium sized aperture and aperture.The aperture characteristics permission molecular diameter of ZSM-5 zeolite is that the paraxylene of 0.63 nanometer spreads rapidly, can seriously hinder ortho-xylene and meta-xylene diffusion that molecular diameter is 0.69 nanometer simultaneously.In the toluene disproportionation process system, there is following relation in the diffusion coefficient of each species in the ZSM-5 duct: benzene 〉=toluene＞ethylbenzene ≈ paraxylene＞ortho-xylene ≈ meta-xylene, this fact means the possibility of toluene disproportionation process being selected the shape selection, can obtain to be higher than in the dimethylbenzene product paraxylene content of isomer of thermodynamical equilibrium concentration far away.
When dimethylbenzene diffused out the duct, though because the difference of diffusion rate makes paraxylene isomer comprises advantage in the dimethylbenzene product, isomerization reaction can further take place in dimethylbenzene near the molecular sieve aperture and on the acid site of outer surface.A shape selectivity is not had in this isomerization reaction, and its speed is far faster than toluene disproportionation speed, so dimethylbenzene also can reach thermodynamical equilibrium very soon and forms.Therefore, if can there be way to suppress the isomerization reaction of dimethylbenzene near the aperture and outer surface acid site, just can improve the para-selectivity of ZSM-5 molecular sieve to toluene disproportionation process.
Modification to the ZSM-5 molecular sieve structure has been proposed among document U.S. Pat 5367099 and the US5607888, promptly reduce near port size and the shielding molecular sieve aperture and the outer surface acidity active sites, the preparation selective disproportionation catalyst of toluene just is based on that above-mentioned principle conceives.The method that realizes is to select the macromolecular compound with thermolysis property for use, be deposited on molecular sieve outer surface by certain method, pass through high-temperature process again, with these macromolecular compound thermal decompositions, be converted into inert coatings, the acid centre of shielding molecular sieve outer surface has also dwindled port size simultaneously to a certain extent.Because the macromolecular compound precursor does not enter in the duct, therefore do not change the acid matter of molecular sieve pore passage inner surface substantially, so just can too not seriously influence the activity of such catalysts generation.What these macromolecular compounds with thermolysis property were generally selected for use is silanes or (gathering) siloxane compound, commonly used is polysiloxane-based, plays modifying function thereby the meeting thermal decomposition under high temperature action of these silicon-containing compounds is converted into siliceous deposits.
The above-mentioned shape processing means of selecting can be that the dystopy method is handled or in-situ method is handled.The dystopy method is meant macromolecular compound is dissolved in the solvent that the catalyst with moulding joins in the solution of being joined again, and then, air-distillation or decompression distillation remove and desolvate, and again catalyst are cooled to room temperature, again roasting.To repeat repeatedly as the above step 1, to obtain having the catalyst of high para-selectivity.In-situ method is meant preformed catalyst is seated in the fixed bed reactors, and macromolecular compound is mixed methylbenzene raw material, under hydroformylation reaction condition is faced in pressurization, catalyst is carried out in-situ treatment.The general reaction in-situ processing time reaches hundreds of hours.With handling time lengthening, activity of such catalysts descends gradually, and para-selectivity progressively rises.As can be seen, these processing method redundant and complicated, it is pretty troublesome to operate.
The objective of the invention is the shortcoming of selecting shape processing troublesome poeration in the document in the past, a kind of preparation method of new selective disproportionation catalyst of toluene is provided in order to overcome.This method has simple to operate, can improve the characteristics of ZSM-5 molecular sieve to the toluene disproportionation process para-selectivity simultaneously.
The objective of the invention is to realize by following technical scheme: a kind of preparation method of selective disproportionation catalyst of toluene in turn includes the following steps:
A) to be made into weight percent concentration be 10～50% solution to the compound that will be selected from Potassium Hydrogen Phthalate, sodium ethylene diamine tetracetate, sulfosalicylic acid sodium salt, potassium tartrate or neopelex, and be heated to 80～100 ℃;
B) adding is carried out ion-exchange through metal-modified ZSM-5 molecular sieve in above-mentioned solution, keeps temperature 1～30 minute;
C) after filtration get required catalyst after washing,, oven dry and the roasting.
In the technique scheme, the metal of metal-modified ZSM-5 molecular sieve is selected from least a in beryllium, magnesium, calcium, strontium, barium, ruthenium, rhodium, palladium, rhenium, platinum, gold, scandium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, cadmium, lanthanum, cerium, tungsten, gallium, tin, antimony or the bismuth, and its load capacity in the ZSM-5 molecular sieve is 0.01～10% by weight percentage.
Xylene isomerization is the same with toluene disproportionation, all is acid catalyzed reaction, and for the ZSM-5 molecular sieve, what this class had been reacted catalytic action mainly is hydroxyl on the aluminum-oxygen tetrahedron.As everyone knows, hydrogen ion on these hydroxyls can be replaced by other monovalent cation by ion-exchange, as ammonium ion, sodium ion, potassium ion etc.,, will lose the activity of this acid catalyzed reaction of paraxylene isomerization if replaced by alkali metal ions such as sodium ion, potassium ions.So, if hydrogen ion or ammonium ion with the hydroxyl position near the ZSM-5 molecular sieve aperture and the outer surface acid site, replace by alkali metal ion by ion-exchange, the isomerization reaction near the aperture and outer surface acid site of dominant para-isomer in the dimethylbenzene that diffuses out the duct is suppressed, thereby improve the para-selectivity of catalyst toluene disproportionation process.
Alkali metal ion can exchange near the ZSM-5 molecular sieve aperture and the hydroxyl position on the outer surface acid site, equally also can exchange the hydroxyl position in the duct.Therefore, near to the aperture and the outer surface acid site on the hydroxyl position exchange in, should try not to exchange the hydroxyl position in the duct, so just can make catalyst when obtaining higher para-selectivity, can also keep the activity suitable toluene disproportionation process.Reach this purpose, can realize by following two aspects:
At first, select the compound or the complex compound of the bigger alkali metal containing ion of those molecular volumes, these species can not or be difficult to enter in the ZSM-5 molecular sieve pore passage, also just not can or less exchange duct in the hydroxyl position.Even the strong electrolyte of the alkali metal containing ion in the aqueous solution, be electrolyzed to produce the anion of alkali metal cation and large volume, because anion can't or be difficult to enter the duct, also can there be static constraint effect to alkali metal cation, make its duct more difficult to get access, thereby exchange the hydroxyl position in the duct as few as possible.
Secondly, select comparatively suitable give-and-take conditions, also can reduce the exchange degree of alkali metal ion as far as possible hydroxyl position in the duct.Solution such as the alkali metal containing ionic species that adopts high concentration carries out the ion-exchange of short period, when alkali metal ion is exchanged the hydroxyl position near the aperture and the outer surface acid site, also has little time to exchange in large quantities hydroxyl position in the duct.
The present invention is in the preparation catalyst for selective disproportionation of toluene, owing to compound or the complex compound of elder generation with the bigger alkali metal containing ion of molecular volume, Potassium Hydrogen Phthalate for example, edetate, sulfosalicylic acid sodium salt, potassium tartrate, neopelex is made into concentrated solution, its weight percent content is 10～50% concentrated solution, generally is the aqueous solution, the also available organic solvent that can dissolve the alkali metal containing ionic species.These materials are difficult to enter in the ZSM-5 molecular sieve pore passage, be the concentrated solution of 10～50% (weight) owing to what adopt again, the time of ion-exchange is shortened greatly, thereby can exchange the hydroxyl position in the duct as few as possible, so just generate the optionally while of paraxylene in improving toluene disproportionation process, catalyst still has high reaction activity and high.The present invention is because only through joining the ion-exchange of solution and short time, therefore operation is simpler, has obtained effect preferably.
The invention will be further elaborated below by embodiment: [embodiment 1]
Get the former powder adding 50 gram Ludox of 80 gram ammonium type ZSM-5 and (by weight percentage, contain SiO
240%) 1.0 gram ammonium molybdate [(NH,
4)
6Mo
7O
244H
2O], 0.85 gram magnesium acetate [Mg (CH
3COO)
24H
2O] and 10 ml waters, mediate extruded moulding, dry back 500 ℃ of following roastings 2 hours, promptly obtain without the preformed catalyst A that selects the shape processing.[embodiment 2]
Getting 10 gram catalyst A, to join temperature be in the solution that is made into of 95 ℃ 4.0 gram neopelexes and 20 ml waters, elimination solution washes with water after 5 minutes, 110 ℃ of dryings, 500 ℃ of following roastings 2 hours obtain the catalyst B that the alkali metal ion exchange process is selected the shape processing.[embodiment 3]
The preparation method just changes neopelex into Potassium Hydrogen Phthalate respectively with embodiment 2, tetrasodium ethylenediamine tetraacetate, and sulfosalicylic acid sodium salt, potassium tartrate obtains catalyst C, D, E, F that the alkali metal ion exchange process is selected the shape processing respectively.[embodiment 4]
With catalyst A～F, on the fixed bed reaction evaluating apparatus, carry out the active and selectivity investigation of toluene disproportionation process.Loaded catalyst is 5.0 grams, and weight space velocity is 4.0 hours
-1, reaction temperature is 425 ℃, and reaction pressure is 2.1MPa, and hydrogen hydrocarbon mol ratio is 2.Appraisal result is as follows:
Table 1
Catalyst is selected shape processing species toluene conversion % paraxylene selectivity %
A is untreated 52.8 24.1
B neopelex 31.6 90.1
C Potassium Hydrogen Phthalate 29.8 82.9
D tetrasodium ethylenediamine tetraacetate 27.5 91.4
E sulfosalicylic acid sodium salt 35.7 80.3
F potassium tartrate 30.4 78.8
Claims (2)
1, a kind of preparation method of selective disproportionation catalyst of toluene may further comprise the steps successively:
A) to be made into weight percent concentration be 10～50% solution to the compound that will be selected from Potassium Hydrogen Phthalate, sodium ethylene diamine tetracetate, sulfosalicylic acid sodium salt, potassium tartrate or neopelex, and be heated to 80～100 ℃;
B) adding is carried out ion-exchange through metal-modified ZSM-5 molecular sieve in above-mentioned solution, keeps temperature 1～30 minute;
C) after filtration get required catalyst after washing,, oven dry and the roasting.
2, according to the preparation method of the described selective disproportionation catalyst of toluene of claim 1, the metal that it is characterized in that metal-modified ZSM-5 molecular sieve is selected from least a in beryllium, magnesium, calcium, strontium, barium, ruthenium, rhodium, palladium, rhenium, platinum, gold, scandium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, cadmium, lanthanum, cerium, tungsten, gallium, tin, antimony or the bismuth, and its load capacity in the ZSM-5 molecular sieve is 0.01～10% by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00119771A CN1126603C (en) | 2000-08-29 | 2000-08-29 | Process for preparing selective disproportionation catalyst of toluene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00119771A CN1126603C (en) | 2000-08-29 | 2000-08-29 | Process for preparing selective disproportionation catalyst of toluene |
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| CN1126603C true CN1126603C (en) | 2003-11-05 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462949B (en) * | 2007-12-17 | 2013-06-19 | 天津市化学试剂研究所 | Method for preparing primary standard reagent potassium hydrogen phthalate |
| CN103769201A (en) * | 2014-01-16 | 2014-05-07 | 东南大学 | Anti-coking modification method for biomass catalytic pyrolysis catalyst ZSM-5 molecular sieve |
| CN110498425A (en) * | 2018-05-17 | 2019-11-26 | 中国科学院大连化学物理研究所 | A kind of method of selective modification zeolite molecular sieve outer surface acidity |
| CN114768879B (en) * | 2022-05-12 | 2023-06-02 | 农业农村部环境保护科研监测所 | Sulfosalicylic acid zirconium-containing hybrid material and preparation method and application thereof |
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