CN1121904C - Shape selective modification method of zeolite catalyst - Google Patents
Shape selective modification method of zeolite catalyst Download PDFInfo
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- CN1121904C CN1121904C CN99110819A CN99110819A CN1121904C CN 1121904 C CN1121904 C CN 1121904C CN 99110819 A CN99110819 A CN 99110819A CN 99110819 A CN99110819 A CN 99110819A CN 1121904 C CN1121904 C CN 1121904C
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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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
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- 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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Abstract
The present invention relates to a shape selective modification method of a zeolite catalyst, which comprises the step of immersing a zeolite catalyst of which the active ingredient is ZSM-5 by silicone of which the molecular weight is from 300 to 4000 for 1 to 60 hours, and the steps of filtration, drying operation and calcination. The silicone is mainly selected from plydimethyl siloxane and poly hydroxymethyl siloxane. The catalyst made by the modification method is suitable for arene disproportionation reaction, and is particularly suitable for using toluene disproportionation for preparing benzene and paraxylene. The toluene conversion rate of the modified catalyst can be 31 weight percentages, and the paraxylene selectivity is 95 weight percentages.
Description
The present invention is a kind of shape-selection and modification method of zeolite catalyst, specifically, be with silicon compound to zeolite type aromatic disproportion catalyst, particularly the selective disproportionation of toluene catalyst that generates paraxylene carries out the method for shape-selection and modification.
Paraxylene is the important source material of polyester industrial.Industrial utilization reformation gasoline, drippolene and toluene disproportionation and transalkylation generate the C in the oil
8Aromatic hydrocarbons is produced paraxylene through isomerization and adsorbing separation or Crystallization Separation.The industrial utilization rate of toluene is relatively low, except that part is used as solvent, and most of toluene and C
9Aromatic hydrocarbons is produced dimethylbenzene by traditional disproportionation processes, and the paraxylene concentration in the disproportionated reaction product is controlled by thermodynamics, and productive rate is lower.
In toluene disproportionation process, increase paraxylene optionally effective ways is that zeolite catalyst is carried out shape-selection and modification.As disclosing the method that a kind of methylbenzene shape selective disproportionation generates paraxylene among the CN1100402A, this method is to contact with zeolite catalyst at the toluene that reaction will contain the agent of paraxylene selectionization the initial phase, catalyst is carried out original position adjustment selectionization, the agent of paraxylene selectionization is organo-silicon compound, mainly is selected from polysiloxanes and silanes material.The selection agent of using in the example of this patent is the comparatively complicated materials of structure such as the mixture of polyphenyl methyl siloxane and dimethyl silicone polymer or methyl hydrogen cyclosiloxane, hexamethyl hydrogen cyclosiloxane, diphenyl silane.The mode of adjusting selectionization is at the reaction initial period, the toluene that will contain the selectionization agent feeds the reactor that catalyst is housed, catalyst is carried out in-situ processing, stop bringing Selection In agent again after making catalyst have required paraxylene selectivity and toluene level of conversion.This on-the-spot selectionization of adjusting need continue 50～300 hours, and the time of selectionization phase is longer.If before adjusting selectionization, catalyst is carried out preselectedization processing, will make the adjustment selectionization phase foreshorten to 28 hours.Described preselectedization processing is with silicon compound, is dissolved in the organic solvent as polyphenyl methyl siloxane, adds zeolite catalyst again, dry, roasting.
Adopting the processing of original position adjustment selectionization in the said method is to act on zeolite surface deposition one by thermal decomposition to contain silicon coating, and this original position adjustment selectionization method needs the long selection time just can make catalyst reach industrial acceptable paraxylene selectivity and toluene conversion.In addition, for industrial bigger device, adjust the selectionization effect and be difficult to accurate prediction, operate wayward.
A kind of method that silica and alumina molar ratio are carried out modification less than the shape selective of 500 aluminosilicate zeolite catalyst is disclosed among the CN1124950A.This method is that catalyst is carried out at least twice dystopy selectionization processing, and wherein the step of dystopy selectionization processing is earlier catalyst to be contacted with the selection agent that is dissolved in organic facies or aqueous phase each time, then catalyst is carried out roasting.Selection agent wherein mainly is selected from siloxane polymer or amino containing silane, as 3,5-dimethylphenyl methyl polysiloxane (Dow-550) or n-pro-pyl amine silane polymer (Hydrosil2627).If the selectionization agent is selected from siloxane polymer, need it is dissolved in the organic facies, this organic facies is a kind of alkane that contains 7 carbon atoms, as dodecane.If the selectionization agent is an amino containing silane, then it is diluted to the aqueous solution, with this solution impregnation zeolite catalyst it is carried out the shape modification again.The processing of this dystopy selectionization wants just can make more than the triplicate catalyst to have good catalytic performance, as using the 3,5-dimethylphenyl methyl polysiloxane to HZSM-5/SiO in this patent example 4
2Carry out 4 dystopys continuously and handle, then at 484 ℃, 3550KPa, hydrogen-hydrocarbon ratio are 2, and the little hourly space velocity of toluene feed weight is to carry out toluene disproportionation process under 4 the condition, and when its result was 25% when toluene conversion, the para-selectivity of catalyst was 86%.This patent also will be carried out the catalyst of dystopy selectionization processing through said method, carry out the processing of in-situ conditioning selectionization before carrying out toluene disproportionation process again, with further raising paraxylene selectivity.
Said method complex operation, catalyst need could to obtain para-selectivity relatively preferably through dystopy selectionizations processing repeatedly, and the processing of dystopy selectionization all will be passed through two-stage roasting at every turn, and in temperature-fall period need N
2Protection.As obtaining better treatment effect, after the processing of dystopy selectionization, adopt steam treatment or the processing of carbon distribution selectionization in addition.
USP5,610,112 have proposed a kind of method that molecular sieve catalyst through preselected modification is carried out modification.This method will have the zeolite catalyst of binding agent or binder free to handle with the first silicon source, and this processing is called preselectedization, the silicon compound of preselectedization use is selected from silane, siloxanes and organic amino group silane polymer, afterwards the catalyst of preselectedization modification is carried out roasting being no more than under 600 ℃ the temperature, then at 200～400 ℃, with 5～100%, 50～100% steam treatment preferably.Do not carry out steam treatment or only carry out simple steam treatment if only carry out preselected processing, selection of catalysts just can not improve, or even harmful.This patent is further to improve the selectivity of paraxylene, and also the catalyst to modification carries out original position adjustment selectionization before disproportionated reaction, and adjusting the selectionization agent is the copolymer (Dow-550) of benzyl silicon and dimethyl-silicon.Catalyst after above step process is at 466 ℃, 3.55MPa, 4WHSV and H
2/ HC is under 2 the condition, and toluene conversion is 30.9%, the paraxylene selectivity is 90.2%.
The dystopy selectionization processing method that the purpose of this invention is to provide a kind of zeolite catalyst, the easy and simple to handle and catalyst that obtain of this method not only has high reaction activity and high, also has good para-selectivity and activity stability.
The shape-selection and modification method of catalyst provided by the invention comprises that with described zeolite catalyst molecular weight be dry, the roasting after 1～60 hour of 300～4000 polysiloxanes dipping.
The described zeolite catalyst of the inventive method is to be the catalyst of active component with the zeolite, can not contain or contain binding agent in the catalyst.Zeolite in the catalyst is selected from the zeolite with intermediate pore size, and as ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-5, preferred ZSM-5 is as the activity of such catalysts component.Binding agent in the catalyst is selected from porous inorganic oxide or clay, suitable inorganic oxide comprises silica, aluminium oxide, zirconia, magnesia, thorium oxide, titanium dioxide, suitable clay comprises bentonite, diatomite, attapulgite, and most preferred binding agent is a silica.
Described catalyst preferably contains binding agent, and preferred catalyst is formed the preferred ZSM-5 of its mesolite, the preferred silica of binding agent by the zeolite of 45～90 heavy % and the binding agent of 10～55 heavy %.The exist kenel of described zeolite in catalyst is Hydrogen.
The silica alumina ratio of described ZSM-5 zeolite, promptly the mol ratio of silica and aluminium oxide should be controlled at 15～150, and preferred 20～60.If the silica alumina ratio of ZSM-5 is too big, the gained activity of such catalysts will descend.
Preparation can directly mix HZSM-5 during catalyst with silica, roasting after the moulding, but during the preparation bar shaped catalyst, carry out easily in order to make extrusion, need to add the extrusion aid sesbania powder that accounts for HZSM-5 and silica gross weight 3～5%, after sesbania powder and silica and HZSM-5 mixed, add water again, preferably add silica aqueous solution and mix and pinch, and then extruded moulding.Mixing the water of adding when pinching or the ratio of silica aqueous solution and solid matter gross mass is 0.8～1.2: 1, contains the silica of 10～50 heavy % in the silica aqueous solution.Particle after extrusion is shaped, 110～250 ℃ of dryings 1～3 hour, 450～600 ℃ of roastings made catalyst in 3～8 hours.
HZSM-5 used in the above-mentioned method for preparing catalyst is made by NaZSM-5 roasting after the ammonium exchange.The ammonium exchange adopts method well known to those skilled in the art to carry out, and as adopting the ammonium salt solution impregnated zeolite, promptly makes HZSM-5 350～550 ℃ of roastings then.
For further removing the metal cation in the catalyst, the catalyst that before with the polysiloxanes dipping, preferably makes with the ammonium salt solution dipping again.Ammonium exchange is preferably carried out under 85～100 ℃ the temperature in room temperature～120 ℃, and used ammonium salt is selected from ammonium chloride or ammonium nitrate, and the weight ratio of HZSM-5 zeolite is 0.02～0.5: 1 in ammonium salt and the catalyst.During the ammonium exchange, ammonium salt should be made into concentration is 2～20 heavy %, and preferably the solution of 5～15 heavy % is used this solution impregnation catalyst 1～6 hour then.Ammonium exchange back gained solid washs to filtrate with deionized water does not have Cl
-, 110～250 ℃ of dryings 1～3 hour, 350～550 ℃ of roastings 1～8 hour are preferably 1～4 hour.
Catalyst that said method makes or the catalyst that exchanges through ammonium directly flood modification with polysiloxanes, and described polysiloxanes has the repetitive that following general formula is expressed:
In the formula, R
1, R
2Can be identical or different, be selected from hydrogen, C respectively
1～C
10Alkyl or hydroxyl, preferred C
1～C
3Alkyl or hydroxyl.Comparatively preferred polysiloxanes is dimethyl silicone polymer or poly-methyl hydroxyl siloxanes.
The molecular weight of described polysiloxanes is 300～4000, is preferably 1000～2000.The molecular weight of control polysilane oxygen alkane is in order to control the viscosity of polysiloxanes, the viscosity that is to say the polysiloxanes that is used for shape-selection and modification is big more, molecular weight surpasses 4000, in dipping process, polysiloxanes just can not be adsorbed on the outer surface of catalyst granules equably, easily forms at the catalyst member outer surface and piles up, cause the activated centre on the catalyst member outer surface not to be capped, in the time of will causing shape-selective disproportionation reaction, toluene conversion is higher, and the paraxylene selectivity is on the low side.Accordingly, because catalyst is after flooding with polysiloxanes, filter, could use after dry, the roasting, if the polysiloxanes viscosity of impregnated catalyst is too small, molecular weight is less than 400, the polysiloxanes that is adsorbed in the catalyst outer surface during filtration runs off easily, causes adverse effect also can for the shape-selection and modification effect of catalyst.
The liquid-solid mass ratio preferred 0.8～1.2: 1 of above-mentioned polysiloxanes that is used to flood and catalyst if the amount of the polysiloxanes that uses is too big, can be made troubles to operation, and cause the waste of polysiloxanes.Dipping is at room temperature to leave standstill 1～60 hour, is preferably 8～36 hours, filter after the dipping, and 90～120 ℃ of dryings 3～8 hours, 250～600 ℃, best 450～600 ℃ of roastings 4～12 hours, preferred 4～6 hours of roasting time promptly gets modified catalyst.
The described polysiloxanes that is used for modification can be recycled, and the number of times of silicon modification can carry out more than twice or twice as required, and the modification number of times is 1～2 time preferably.After each silicon modification, catalyst all needs dry, roasting.
Catalyst with the inventive method modification is applicable to the aromatic hydrocarbons shape-selective disproportionation reaction, especially is fit to methylbenzene shape selective disproportionation and produces benzene and paraxylene.The condition of disproportionated reaction is: 400～460 ℃ of temperature, pressure 0.5～2.0MPa, toluene feed weight space velocity 1～5 hour
-1, hydrogen and charging toluene volume ratio be 100～500.Products therefrom and Separation of Benzene and paraxylene are reclaimed in the reaction back.
The inventive method is directly carried out shape-selection and modification with modifier to catalyst, again catalyst is not carried out modification and do not need modifier is dissolved in any solvent, catalyst only need carry out the processing of 1～2 dystopy selectionization, can be directly used in the methylbenzene shape-selective disproportionation reaction, need not again catalyst to be carried out the processing of original position adjustment selectionization, just can reach than the prior art catalyst is high toluene conversion and paraxylene selectivity.For example 450 ℃, 1.2MPa, toluene feed weight space velocity 3 hours
-1, H
2With volume of toluene than being under 300 the condition, through 1500 hours running, toluene conversion reached 95 heavy % greater than 30 heavy %, paraxylene selectivity.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
This example carries out the silicon modification with the inventive method to catalyst.
With silica alumina ratio is 25 HZSM-5 zeolite powder (the two three doses of manufactories of magnificent petrochemical industry in Wenzhou) and silicon dioxide powder by 85: 15 weight ratio mixing, the sesbania powder that will account for HZSM-5 and silica gross weight 3% again adds wherein, be fully mixed to even, Ludox (Fushun No.3 Petroleum Factory's catalyst plant) aqueous solution that adds powder total amount 95% mixes to be pinched and extruded moulding, and concentration of silicon dioxide is 30 heavy % in the silica aqueous solution.110～120 ℃ of dryings of the solid that extruded moulding obtains 3 hours, 500 ℃ of roastings 5 hours make catalyst a.
Getting 100 gram catalyst a, under 90 ℃, is the aqueous ammonium chloride solutions dipping of 10 heavy % with concentration, carries out ion-exchange twice, and the amount of each used aqueous ammonium chloride solution is 120 grams, 1 hour swap time, and filtration, solid washs to filtrate with deionized water does not have Cl
-, 110～120 ℃ of dryings 2 hours, 500 ℃ of roastings are 4 hours in the air.
Get the catalyst of above-mentioned ammonium exchange, under the room temperature, in 1.2: 1 ratio of liquid-solid mass ratio, be 1200, be dimethyl siloxane (the Shandong Da Yi chemical industry joint-stock company) dipping 12 hours of liquid under the room temperature with molecular weight, filter, 110 ℃ of dryings 2 hours, 550 ℃ of roastings are 3 hours in the air, modified catalyst A.
Getting 6 gram catalyst A and pack in the stainless steel tubular type reactor, is reaction raw materials with the pure toluene 440 ℃, 1.0MPa, toluene feed weight space velocity 3 hours
-1, carry out toluene disproportionation process under hydrogen and the operating condition of volume of toluene than 400: 1.The results are shown in Table 1.
Example 2
This example carries out the silicon modification with the inventive method to catalyst, but silicon modification procatalyst does not carry out the ammonium exchange.
Get the 20 catalyst a that make of gram examples 1, under the room temperature, in 1.2: 1 ratio of liquid-solid mass ratio, with molecular weight be 1200, the dimethyl siloxane that is liquid under the room temperature flooded 12 hours, filter, 120 ℃ of dryings 2 hours, 550 ℃ of roastings are 4 hours in the air, modified catalyst B.
Get 6 gram catalyst B, carry out the toluene disproportionation experiment, the results are shown in Table 1 according to the reaction condition of example 1.By table 1 data as seen, the catalyst A of carrying out ammonium exchange before the silicon modification is higher slightly than the catalytic activity of not carrying out the catalyst B that ammonium exchanges.
Example 3
The employing silica alumina ratio is 60 HZSM-5 zeolite, prepares catalyst and carries out the silicon modification according to example 1 described method, obtains modified catalyst C.Get 6 gram catalyst C, carry out toluene disproportionation process by the condition of example 1, reaction result sees Table 1.
From table 1 data as can be seen, the silica alumina ratio of the HZSM-5 zeolite that the preparation catalyst adopts increases, and toluene conversion reduces.
Example 4
This example carries out the modification of secondary silicon to catalyst.
Get the catalyst A of example 1 method preparation, under the room temperature, in 1.2: 1 ratio of liquid-solid mass ratio, with molecular weight be 1200, the dimethyl siloxane that is liquid under the room temperature flooded 12 hours, filter, 110～120 ℃ of dryings, 550 ℃ of roastings are 3 hours in the air, twice-modified catalyst D.
Carry out toluene disproportionation process by example 1 described reaction condition, result of the test sees Table 1.Table 1 data show catalyst carried out the modification of secondary silicon after, than the catalyst A of a silicon modification, the activity of catalyst D descends slightly, but the selectivity of paraxylene improves a lot.
Example 5～6
Following example selects for use the dimethyl silicone polymer of different molecular weight that catalyst is carried out the silicon modification.
Method according to example 1 prepares modified catalyst, and different is, and example 5 adopts that molecular weight are that 2000 dimethyl silicone polymer is a modifier, and it is that 1000 dimethyl silicone polymer is a modifier that example 6 adopts molecular weight.Reaction condition by example 1 carries out toluene disproportionation process then, and result of the test sees Table 2.
Example 7～11
Following case expedition HZSM-5 content is to the influence of catalyst performance.
Prepare catalyst according to example 1 described method, different is the content difference of HZSM-5 in catalyst in each example, and the catalyst that makes carries out toluene disproportionation process by the reaction condition of example 1.The weight percent of the HZSM-5 that contains in each example catalyst when reaction result sees Table 3.As shown in Table 3, along with the increase of catalyst mesolite ratio, toluene conversion raises gradually, and catalyst activity strengthens, but the paraxylene selectivity descends gradually in the product.
Example 12
This example uses methyl hydroxyl siloxanes as modifier catalyst to be carried out the silicon modification.
Method by example 1 prepares catalyst, and different is with molecular weight is that 1200 poly-methyl hydroxyl siloxanes replaces dimethyl silicone polymer.Reaction condition by example 1 carries out the toluene disproportionation process test again, and reaction result is: paraxylene concentration 12.33 heavy %, paraxylene selectivity 88.88 heavy % in toluene conversion 30.88 heavy %, the product.
Example 13
This example is investigated the cycling and reutilization of silica modifier.
Method by example 1 prepares modified catalyst, and different is with remaining dimethyl silicone polymer after the silicon modification is that circulation modifier carries out the silicon modification.Reaction condition by example 1 carries out the toluene disproportionation process test then, and experimental result is: paraxylene concentration 12.53 heavy %, paraxylene selectivity 88.56 heavy % in toluene conversion 31.18 heavy %, the product.Data show, circulation modifier is basic identical to the modified effect of the modified effect of catalyst and fresh modifier.
Example 14
Method by example 4 is carried out twice silicon modification to catalyst, produces 500 kilograms modified catalyst E.Getting 1 kg catalyst E and pack in the stainless steel tubular type adiabatic reactor, was reaction raw materials with the pure toluene, 450 ℃, 1.2MPa, toluene feed weight space velocity 3 hours
-1, hydrogen and volume of toluene ratio be to carry out the toluene disproportionation process test under 300: 1 the operating condition, holding temperature pressure is constant in the course of reaction.In the test every 24 hours sample analysis once, the toluene conversion that each sample analysis is recorded and be that its mean value mapping is got by unit with 100 hours to two benzene selectives, as shown in Figure 1.Fig. 1 shows, running through 1500 hours, toluene conversion (Tc) is all above 31 heavy %, paraxylene selectivity (PX/ ∑ X) surpasses 95 heavy %, average result is: toluene conversion 31.24 heavy %, paraxylene selectivity 95.48 heavy %, show that this catalyst has good activity, selectivity and stability.
Table 1
| Example | The catalyst numbering | Paraxylene concentration in the product, heavy % | The paraxylene selectivity, heavy % | Toluene conversion, heavy % |
| 1 | A | 12.78 | 88.38 | 31.35 |
| 2 | B | 12.50 | 89.15 | 29.20 |
| 3 | C | 5.16 | 83.36 | 11.35 |
| 4 | D | 13.23 | 96.92 | 30.29 |
Table 2
| Example | The modifier molecules amount | Paraxylene concentration in the product, heavy % | The paraxylene selectivity, heavy % | Toluene conversion, heavy % |
| 5 | 2000 | 10.96 | 75.27 | 34.24 |
| 6 | 1000 | 12.56 | 86.62 | 32.67 |
Table 3
| Example | HZSM-5 content in the catalyst, heavy % | Paraxylene concentration in the product, heavy % | The paraxylene selectivity, heavy % | Toluene conversion, heavy % |
| 7 | 50 | 11.98 | 95.84 | 25.23 |
| 8 | 55 | 13.07 | 92.89 | 29.43 |
| 9 | 60 | 13.47 | 92.39 | 30.82 |
| 10 | 70 | 12.41 | 86.30 | 32.83 |
| 11 | 75 | 10.91 | 70.34 | 37.38 |
Claims (11)
1, a kind of shape-selection and modification method of zeolite catalyst, comprise that with described zeolite catalyst molecular weight be 300～4000 polysiloxanes room temperature dipping 1～60 hour, 90～120 ℃ of dryings in dipping back 3～8 hours, 250～600 ℃ of roastings 4～12 hours, the liquid-solid mass ratio of polysiloxanes that is used to flood and catalyst is 0.8～1.2: 1.
2, in accordance with the method for claim 1, it is characterized in that described zeolite catalyst is is the catalyst of active component with ZSM-5.
3, in accordance with the method for claim 1, it is characterized in that described zeolite catalyst is made up of the silica of the ZSM-5 of 45～90 heavy % and 10～55 heavy %.
4, according to claim 2 or 3 described methods, the silica alumina ratio that it is characterized in that described ZSM-5 is 20～60.
5,, it is characterized in that described polysiloxanes has the repetitive that following general formula is expressed according to described any one method of claim 1～3:
In the formula, R
1, R
2Be selected from hydrogen, C
1～C
10Alkyl or hydroxyl.
6,, it is characterized in that R in the repetitive of polysiloxanes according to described any one method of claim 1～3
1, R
2Be selected from C
1～C
3Alkyl or hydroxyl.
7,, it is characterized in that described polysiloxanes is dimethyl silicone polymer or poly-methyl hydroxyl siloxanes according to described any one method of claim 1～3.
8, according to the described any method of claim 1～3, the molecular weight that it is characterized in that described polysiloxanes is 1000～2000.
9, in accordance with the method for claim 7, the molecular weight that it is characterized in that described dimethyl silicone polymer or poly-methyl hydroxyl siloxanes is 1000～2000.
10,, it is characterized in that zeolite catalyst need all need dry, roasting with described polysiloxanes dipping twice behind each dipping according to described any one method of claim 1～3.
11,, it is characterized in that described zeolite catalyst is with ℃ carrying out ion-exchange, drying, 350～550 ℃ of roastings after the ion-exchange with ammonium salt solution in room temperature～120 earlier before the polysiloxanes dipping according to described any one method of claim 1～3.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110819A CN1121904C (en) | 1999-07-22 | 1999-07-22 | Shape selective modification method of zeolite catalyst |
| DE10035604A DE10035604A1 (en) | 1999-07-22 | 2000-07-21 | Modifying selectivity of zeolite catalyst, e.g. for disproportionation of toluene to p-xylene, involves impregnation with polysiloxane, e.g. poly-dimethylsiloxane, followed by drying and calcination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110819A CN1121904C (en) | 1999-07-22 | 1999-07-22 | Shape selective modification method of zeolite catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1281750A CN1281750A (en) | 2001-01-31 |
| CN1121904C true CN1121904C (en) | 2003-09-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99110819A Expired - Lifetime CN1121904C (en) | 1999-07-22 | 1999-07-22 | Shape selective modification method of zeolite catalyst |
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| CN (1) | CN1121904C (en) |
| DE (1) | DE10035604A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7049260B2 (en) | 2003-06-03 | 2006-05-23 | Chevron Phillips Chemical Company Lp | Selective para-xylene production via methylation of toluene with methanol in the presence of modified HZSM-5 catalyst |
| CN100391609C (en) * | 2004-10-29 | 2008-06-04 | 中国石油化工股份有限公司 | Preparation method of catalyst for paraxylene produced by toluene selective disproporationation |
| CN100430137C (en) * | 2004-10-29 | 2008-11-05 | 中国石油化工股份有限公司 | Preparation method of toluene selective disproportionation catalyst |
| CN100352549C (en) * | 2004-10-29 | 2007-12-05 | 中国石油化工股份有限公司 | Preparation method of catalyst for paraxylene produced by toluene selective disproportionation |
| CN100352548C (en) * | 2004-10-29 | 2007-12-05 | 中国石油化工股份有限公司 | Method for preparing catalyst for toluene selective disproportionation |
| CN100428996C (en) * | 2005-09-29 | 2008-10-29 | 南京工业大学 | Method for preparing toluene disproportionation zeolitic catalyst with increased para-selectivity |
| CN100391915C (en) * | 2006-04-13 | 2008-06-04 | 中国科学院大连化学物理研究所 | Method for on-line modification of catalyst for methylating toluene to produce paraxylene |
| CN101209947B (en) * | 2006-12-27 | 2011-05-18 | 中国石油化工股份有限公司 | Aromatization method for low carbon alkane |
| CN101590423B (en) * | 2008-05-29 | 2011-04-20 | 中国石油化工股份有限公司 | Shape-selection and modification method for zeolite catalyst |
| CN107754848B (en) * | 2016-08-23 | 2020-12-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing p-methyl ethyl benzene by shape-selective catalysis of carbon octaene |
| CN110227546B (en) * | 2018-03-06 | 2022-01-04 | 中国石油化工股份有限公司 | Catalyst for preparing p-xylene by methanol conversion and preparation method thereof |
| CN115368038B (en) * | 2022-08-25 | 2023-07-04 | 安徽海螺制剂工程技术有限公司 | Phosphogypsum-based mineralizer doped with polysiliconol polymer and preparation method of cement clinker thereof |
-
1999
- 1999-07-22 CN CN99110819A patent/CN1121904C/en not_active Expired - Lifetime
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2000
- 2000-07-21 DE DE10035604A patent/DE10035604A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE10035604A1 (en) | 2001-03-01 |
| CN1281750A (en) | 2001-01-31 |
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