CN101885664B - Trimethylbenzene catalytic conversion method - Google Patents
Trimethylbenzene catalytic conversion method Download PDFInfo
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Abstract
The invention relates to a trimethylbenzene catalytic conversion method, mainly solving the problem of low activity in the reaction process of carrying out the trimethylbenzene catalytic conversion with the conventional catalyst. The invention adopts a new method for carrying out the trimethylbenzene catalytic conversion, and in the technical scheme, the catalyst comprises the following components in parts by weight: (a) 5-95 parts of nuclear shell type molecular sieve material, and (b) 95-5 parts of binder; the nuclear phase of the nuclear shell type molecular sieve is ZSM-5 and the shell layer is beta zeolum crystalline grains with the coverage of 50-100%, thus solving the above problems and being applied to industrial production of the trimethylbenzene catalytic conversion.
Description
Technical field
The present invention relates to a kind of method of trimethylbenzene catalytic conversion.
Background technology
Trimethylbenzene mainly refers to 1，2，3-trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene.Reaction in the trimethylbenzene catalytic conversion system comprises disproportionation, transalkylation and isomerization reaction etc., its ultimate aim is the aromatic hydrocarbons total conversion rate that improves the yield of dimethylbenzene and increase trimethylbenzene, and these can be realized by selecting a kind of suitable catalyzer and suitable processing condition.Successively adopt ZSM-5 zeolite, β zeolite etc. as the catalyzer of this reaction system.
The strength of acid of ZSM-5 and sour distribution can in very large range regulate and control.Its crystalline size also can be regulated in the larger context, and the modifiability of structure is large, so ZSM-5 is the molecular screen material that extensively adopts in research.In ZSM-5 molecular sieve, 10 ring straight channel are of a size of 0.51 * 0.55nm, and passage is of a size of 0.54 * 0.56nm in a zigzag, is usually used in the micromolecular cracking reactions such as intracrystalline shape selective catalytic reaction and gasoline fraction.The macromolecular size of aromatic hydrocarbons is generally larger, as 1,3, the molecular dynamics diameter of 5-trimethylbenzene is 0.86nm, 1,2, the molecular dynamics diameter of 4-trimethylbenzene is 0.76nm, can carry out on the ZSM-5 surface so the aromatic hydrocarbons macromole transforms major part, its internal surface acid site utilization ratio is low, so reactive behavior is lower.Due to easy coking and deactivation in reaction, catalyst life is also shorter in addition.
The β zeolite is that find up to now unique has and intersect the macropore three-dimensional structure supersiliceous zeolite of twelve-ring channel system (12 ring windows are of a size of 0.76 * 0.64nm), due to the singularity of its structure, have acid catalysis characteristic and structure selectivity concurrently.It has good heat and hydrothermal stability, appropriate acidity and acid acceptance and hydrophobicity.Its catalytic applications shows the characteristics that hydrocarbon reaction is difficult for coking and long service life, at aspects such as catalytic cracking, disproportionation and transalkylation reactions, shows excellent catalytic performance, is very important catalytic material.Document (Journal ofthe Japan Petroleum Institute, 45:99) finds that also the specific activity ZSM-5 of β zeolite in the conversion reaction of aromatic hydrocarbons macromole is high.But general simple beta-molecular sieve is higher as the catalyzer cost.
In experiment, carried out the performance test of aromatic hydrocarbons conversion reaction after our ZSM-5 and β zeolite mechanically mixing, due to sample strong acidic site comparatively small amt, and external surface area is not high yet, although so reactive behavior higher than ZSM-5, still very low generally.Take ZSM-5 molecular sieve as nuclear phase, β is nanocrystalline is that the core-shell molecular sieve of shell should be highly beneficial to the macromolecular continuous tandem reaction of aromatic hydrocarbons.Macromole cracking in the shell duct be than small molecules after, continue to enter the nuclear phase duct and select shape or other cracking reactions.Usually, also can adopt the method for carried noble metal, improve catalyst activity and stability.But up to the present, the bibliographical information that synthetic this class core-shell material of ZSM-5/ β is seldom arranged, [the Chem.Mater such as Bouizi, 18:4959] ZSM-5/ β has only made brief of the introduction in the article about the synthetic controlling factors of core-shell molecular sieve, but result shows that the coverage of surperficial β shell is very low, be only 5% left and right, low coverage can have a strong impact on reactive behavior.The inventor repeats according to document, and product is carried out performance evaluation, finds that weight space velocity is 1.0 hours
-1, temperature of reaction is 380 ℃, reaction pressure 0.5 MPa, hydrogen hydrocarbon mol ratio is 1,3 of 6.0 ℃ of lower ZSM-5 cores, and 5-trimethylbenzene transformation efficiency is 40%, and the ZSM-5/ beta nuclear shell-shaped molecular sieve of literature method under the same conditions 1,3,5-trimethylbenzene cracking conversion rate is only also 51%.
Summary of the invention
Technical problem to be solved by this invention is the low problem of catalyzer trimethylbenzene catalytic conversion reactive behavior in the past, and a kind of method of new trimethylbenzene catalytic conversion is provided.The method has advantages of that catalyst activity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of trimethylbenzene catalytic conversion take trimethylbenzene as raw material, is 300～550 ℃ in temperature of reaction, and reaction pressure is 0.2～3 MPa, and air speed is 1.0～8.0 hours
-1, under the condition of hydrogen/hydrocarbon mol ratio 1～8: 1, raw material contacts with catalyzer, and product generates toluene, dimethylbenzene and durene, and catalyzer used comprises following component in parts by weight:
A) the ZSM-5/ beta nuclear shell-shaped molecular sieve material of 5～95 parts;
B) binding agent of 95～5 parts;
Wherein the nuclear phase of core-shell type molecular sieve is ZSM-5, and shell is that coverage is 50～100% β zeolite grain.
In technique scheme, β zeolite shell coverage preferable range is 50～90%; Raw material trimethylbenzene preferred version is 1，2，3-trimethylbenzene, 1,2, at least a in 4-trimethylbenzene or 1,3,5-trimethylbenzene; The silica alumina ratio SiO of ZSM-5 nuclear phase
2/ Al
2O
3Preferable range is 20～300; The silica alumina ratio SiO of β zeolite shell
2/ Al
2O
3Preferable range is 15～∞; The weight ratio preferable range of nuclear phase molecular sieve and shell molecular sieve is 0.2～30: 1; The binding agent preferred version be silicon sol, pseudo-boehmite, aluminum oxide or after acid treatment clay at least a, more preferably scheme is silicon sol or gama-alumina; The preferred version of catalyzer is to comprise also in the parts by weight catalyzer that 0.01～30 part is selected from least a metal or the oxide compound that contains in magnesium, molybdenum or platinum, and more preferably scheme is to comprise also in the parts by weight catalyzer that 0.05～5 part is selected from least a metal or the oxide compound that contains in magnesium, molybdenum or platinum.
In technique scheme, be used for the preparation method of trimethylbenzene catalytic conversion catalyzer, comprise the following steps:
A) add in the ZSM-5/ of aequum beta nuclear shell-shaped molecular sieve the binding agent of aequum and aequum be selected from least a compound kneading in containing magnesium, molybdenum or platinum, moulding, drying after obtain catalyst Precursors; Or obtain the catalyst Precursors precursor after the ZSM-5/ beta nuclear shell-shaped molecular sieve of aequum being added the binding agent kneading, moulding, drying of aequum, the catalyst Precursors precursor is contained at least a compound loaded to the catalyst Precursors precursor in magnesium, molybdenum or platinum with pickling process with being selected from of aequum, obtain catalyst Precursors after drying;
B) catalyst Precursors that a) step is obtained carries out roasting under air atmosphere, oxygen-lean atmosphere or oxygen-enriched atmosphere, speed with 0.1～20 ℃/minute is warming up to 300～700 ℃, kept 0.5～10 hour, and made metallic compound be converted into metal oxide, obtain catalystic material after cooling.
In technique scheme, the synthetic method of the beta nuclear shell-shaped zeolite molecular sieve of ZSM-5/ can be selected from following method preparation, as comprise the following steps:
A) concentration expressed in percentage by weight that the ZSM-5 zeolite of aequum is joined aequum under 20～95 ℃ is in 0.1～10% cationoid reagent solution, after filtering ZSM-5 zeolite I; The concentration expressed in percentage by weight of ZSM-5 zeolite I being put into aequum under 20～95 ℃ is in 0.1～10% β particle solution, after filtration, after drying the mixture I of ZSM-5 zeolite and β zeolite;
B) silicon source, aluminium source and template R are mixed to get the synthetic liquid of alkalescence of PH＞9, mole proportioning of synthetic liquid is: R/SiO
2=0.02～15, H
2O/SiO
2=4～400, SiO
2/ Al
2O
3=30～∞, M
2O/SiO
2=0～3, M is Na or K;
C) synthesize to above-mentioned alkalescence the mixture I that adds (a) step to obtain in liquid, obtain mixed solution I I; Wherein in the add-on of mixture I and synthetic liquid, the mass ratio of contained silicon-dioxide is 0.5～20: 1;
D) with above-mentioned mixed solution I I in 80～200 ℃ of lower crystallization 2.5～240 hours;
E) crystallization finishes by filtration, washing, ammonium exchange, drying, and getting nuclear phase is ZSM-5, and shell is the beta nuclear shell-shaped zeolite molecular sieve of the ZSM-5/ of β zeolite, and wherein the shell coverage is 50～100%;
Wherein in (a) step, cationoid reagent is selected from least a in polymethylmethacrylate, diallyl dimethyl ammoniumchloride pyridine dicarboxylic acid, ammoniacal liquor, ethamine, n-Butyl Amine 99, tetraethyl ammonium hydroxide, TPAOH, tetraethylammonium bromide, 4-propyl bromide, TBAH; (b) in step, the silicon source is selected from least a in water glass, silicon sol, water glass, white carbon black or atlapulgite; The aluminium source is selected from Tai-Ace S 150, sodium aluminate, aluminum isopropylate, aluminum chloride or γ-Al
2O
3In at least a; Template R is selected from least a in Sodium Fluoride, Neutral ammonium fluoride, tetraethyl ammonium hydroxide, tetraethylammonium bromide.
ZSM-5 molecular sieve is due to the restriction of pore structure, and internal surface acid site utilization ratio is low and make its activity in the trimethylbenzene catalytic conversion reaction lower; Beta-molecular sieve has suitable strength of acid and acid amount, and macroporous structure is conducive to the diffusion of trimethylbenzene molecule simultaneously, can effectively improve the trimethylbenzene catalytic conversion ability, but use cost is higher; Although the trimethylbenzene activity of conversion of ZSM-5 and β zeolite mechanically mixing sample is higher than ZSM-5, still very low generally; Reactive behavior with the beta nuclear shell-shaped zeolite molecular sieve of ZSM-5/ of the low β shell coverage (5%) of literature method preparation is not high equally.The method that is used for trimethylbenzene catalytic conversion that the present invention relates to, at least a in water glass cheap and easy to get, silicon sol, water glass, white carbon black or the atlapulgite as the silicon source, prepared the beta nuclear shell-shaped zeolite molecular sieve of ZSM-5/ with high shell coverage (50～100%), so its reactive behavior can be improved significantly.In addition, in this Catalysts and its preparation method, also added a certain amount of metal component, the increase of activity has been had promoter action.When adopting catalyzer of the present invention to be used for the trimethylbenzene catalytic conversion reaction, what feed stock conversion was higher reaches 90%, has obtained technique effect preferably.
The present invention is further elaborated below by embodiment.
Embodiment
[comparative example 1]
Comparative example 1 is used for illustrating SiO
2/ Al
2O
3Be preparation and the corresponding toluene methylation reactivity worth thereof of synthetic, the catalyzer (body catalyst and metal-modified catalyzer) of 100 ZSM-5 molecular sieve.Concrete reactant ratio and experimental technique are as follows:
Can obtain ZSM-5 zeolite Zeolite synthesis system after 124 gram water glass, 2.9 gram Tai-Ace S 150,18 gram sodium-chlor, 6 milliliters of sulfuric acid, 20 milliliters of ethamine, 10 milliliters of ammoniacal liquor and the even plastic of 600 ml waters.This mixed system moves in teflon-lined stainless steel crystallizing kettle, and in 170 ℃ of baking ovens, static crystallization can obtain zeolite molecular sieve product ZB-1 in 48 hours.The characteristic diffraction peak that the XRD figure spectrum of sample has the ZSM-5 zeolite molecular sieve is without the stray crystal peak; Chemical analysis records SiO
2/ Al
2O
3Be 100.
With zeolite molecular sieve product ZB-1, the ammonium chloride solution with 20%, repeats 4 times by liquid-solid ratio exchange in 4: 14 hours, suction filtration, washing, drying in 95 ℃, obtains zeolite molecular sieve product ZBN-1.Take silicon sol as binding agent, with 22 gram zeolite molecular sieve product ZBN-1,14 gram silicon sol, 0.3 gram sesbania powder and 5 ml waters, mixing is mediated, extruded moulding, and 540 ℃ of roasting 2h make Hydrogen ZSM molecular sieve catalyst HZB-Cat1.
Take silicon sol as binding agent, with 22 gram zeolite molecular sieve product ZBN-1,14 gram silicon sol, 3.2 gram magnesium nitrates, 0.3 gram sesbania powder and 5 ml waters, mixing is mediated, extruded moulding, and 540 ℃ of roasting 2h make modified ZSM-5 molecular sieve catalyst MZB-Cat1.
Carry out the active investigation of 1,2,4 trimethylbenzene catalytic cracking reactions on the fixed bed reaction evaluating apparatus.Loaded catalyst is 3.0 grams, and weight space velocity is 1.0 hours
-1, temperature of reaction is 420 ℃, reaction pressure 0.5 MPa, and hydrogen hydrocarbon mol ratio is 6.0.Reaction result can be calculated: 1,2, the 4 trimethylbenzene transformation efficiencys of Hydrogen ZSM molecular sieve catalyst HZB-Cat1 are 40.0%; 1,2, the 4 trimethylbenzene transformation efficiencys of ZSM-5 Type Zeolites agent MZB-Cat1 are 48.3%.
[comparative example 2]
Comparative example 2 is used for illustrating SiO
2/ Al
2O
3Be preparation and corresponding heavy aromatic hydrocarbon light and the transalkylation reaction performance of synthetic, the catalyzer (body catalyst and metal-modified catalyzer) of 80 beta-molecular sieve.Concrete reactant ratio and experimental technique are as follows:
Can obtain the beta-zeolite molecular sieve synthetic system after 24 gram white carbon blacks, 0.5 gram sodium aluminate, 18 gram sodium-chlor, 6 milliliters of sulfuric acid, 25 milliliters of tetraethyl ammonium hydroxides and the even plastic of 600 ml waters, subsequently with mother liquor 160 ℃ of hydrothermal crystallizings 72 hours, washing, drying obtain product ZB-2.The XRD figure spectrum of gained sample has the characteristic diffraction peak of beta-zeolite molecular sieve; Chemical analysis records SiO
2/ Al
2O
3Be 80.
With zeolite molecular sieve product ZB-2, after temperature-programmed calcination took off organic amine, the ammonium chloride solution with 20%, repeated 4 times by liquid-solid ratio exchange in 4: 14 hours, suction filtration, washing, drying in 95 ℃, obtains zeolite molecular sieve product ZBN-2.Take aluminum oxide as binding agent, with 20 gram zeolite molecular sieve product ZBN-2,17 gram aluminum oxide, 1 milliliter of concentrated nitric acid, 0.3 gram sesbania powder and 17 ml waters, mixing is mediated, extruded moulding, and 540 ℃ of roasting 2h make Hydrogen beta-molecular sieve catalyzer HZB-Cat2.
Take aluminum oxide as binding agent, with 20 gram zeolite molecular sieve product ZBN-2,17 gram aluminum oxide, 1 milliliter of concentrated nitric acid, 2.5 gram ammonium molybdates, 0.3 gram sesbania powder and 17 ml waters, mixing is mediated, extruded moulding, 540 ℃ of roasting 2h make modified beta molecular sieve catalyzer MZB-Cat2.
Carry out the active investigation of 1,2,3 trimethylbenzene catalytic cracking reactions on the fixed bed reaction evaluating apparatus.Loaded catalyst is 3.0 grams, and weight space velocity is 3.0 hours
-1, temperature of reaction is 550 ℃, reaction pressure 3.0 MPas, and hydrogen hydrocarbon mol ratio is 1.0.Reaction result can be calculated: 1,2, the 3 trimethylbenzene transformation efficiencys of Hydrogen beta-molecular sieve catalyzer HZB-Cat2 are 88.9%; 1,2, the 3 trimethylbenzene transformation efficiencys of modified beta molecular sieve catalyzer MZB-Cat2 are 89.2%.
[comparative example 3]
Comparative example 3 is used for explanation, with reference to Bouizi etc. at document [Chem.Mater, 18:4959] in the method reported, take tetraethyl orthosilicate synthesizing as the synthetic ZSM-5/ beta nuclear shell-shaped molecular sieve in silicon source, body and modified catalyst have been prepared, and it is carried out 1,3,5-trimethylbenzene conversion reaction performance evaluation.Concrete reactant ratio and experimental technique are as follows:
The reactant ratio of nuclear phase crystal seed: 0.6K
2O: 0.25 (TPA)
2O: 0.2Al
2O
3: 1SiO
2: 30H
2O
The reactant ratio that β is nanocrystalline: 4.5 (TEA)
2O: 0.25Al
2O
3: 25SiO
2: 295H
2O
The reactant ratio of nucleocapsid diauxic growth: 4.5 (TEA)
2O: 0.25Al
2O
3: 25SiO
2: 295H
2O
211 gram tetraethyl orthosilicate solution are dissolved in 200 gram water, are configured to solution A; 407 gram TPAOH solution (concentration 25%) are dissolved in 100 gram water, are configured to solution B; 104 gram vitriolate of tartar are dissolved in 240 gram water, are configured to solution C.Solution B is slowly dropped in solution A, fully stir, then add solution C, the reaction mixture of formation 170 ℃ of crystallization 2 days, obtains the nuclear phase ZSM-5 crystal seed I of large crystal grain.
5282 gram tetraethyl orthosilicate solution are dissolved in 2300 gram water, are configured to solution A; 1326 gram tetraethyl ammonium hydroxide solution (concentration 25%) are dissolved in 1000 gram water, are configured to solution B; 41 gram sodium aluminate solutions in 2200 gram water, are configured to solution C.With solution A, B and C, abundant stirring and evenly mixing, the reaction mixture of formation 80 ℃ of crystallization 15 days, obtains the nanocrystalline II of β.
The filtrate oven drying at low temperature of the nuclear phase ZSM-5 crystal seed I that obtains is joined in the nanocrystalline II suspension liquid of β that the 0.5wt% deionized water disperses again, stick 30min, after filtering drying in 540 ℃ (3 ℃/min) lower roasting 5h makes nanosized seeds firmly be attached on the ZSM-5 surface, and with this as core crystal seed III.
5282 gram tetraethyl orthosilicate solution are dissolved in 2300 gram water, are configured to solution A; 1326 gram tetraethyl ammonium hydroxide solution (concentration 25%) are dissolved in 1000 gram water, are configured to solution B; 41 gram sodium aluminate solutions in 2200 gram water, are configured to solution C.With solution A, B, C and core crystal seed III, abundant stirring and evenly mixing, the reaction mixture of the nucleocapsid diauxic growth that forms, 140 ℃ of crystallization 3 days, obtain zeolite molecular sieve III, numbering ZB-3, characterize through SEM spectrogram and XRD, can think that the described ZSM-5/ beta nuclear shell-shaped molecular sieve of synthetic materials and document is consistent, have hud typed structure, its shell phase coverage is about 5%.
To obtain zeolite molecular sieve ZB-3 product, in 550 ℃ (3 ℃/min) lower roasting 6h is with removed template method, use 20% ammonium chloride solution in 95 ℃ again, by liquid-solid ratio exchange in 4: 14 hours, suction filtration, washing, drying, repeat 4 times, obtain zeolite molecular sieve ZBN-3 product.Take aluminum oxide as binding agent, with 20 gram zeolite molecular sieve ZBN-3 products, 17 gram aluminum oxide, 1 milliliter of concentrated nitric acid, 0.3 gram sesbania powder and 17 ml waters, mixing is mediated, extruded moulding, 540 ℃ of roasting 2h make Hydrogen ZSM-5/ beta nuclear shell-shaped molecular sieve catalyzer HZB-Cat3.
Take aluminum oxide as binding agent, with 20 gram zeolite molecular sieve product ZBN-3,17 gram aluminum oxide, 1 milliliter of concentrated nitric acid, 2.5 gram ammonium molybdates, 0.3 gram sesbania powder and 17 ml waters, mixing is mediated, extruded moulding, 540 ℃ of roasting 2h make modified ZSM-5/beta nuclear shell-shaped molecular sieve catalyzer MZB-Cat3.
Carry out the active investigation of 1,3,5 trimethylbenzene catalytic cracking reactions on the fixed bed reaction evaluating apparatus.Loaded catalyst is 3.0 grams, and weight space velocity is 1.0 hours
-1, temperature of reaction is 300 ℃, reaction pressure 0.2 MPa, and hydrogen hydrocarbon mol ratio is 6.0.Reaction result can be calculated: 1,3, the 5 trimethylbenzene transformation efficiencys of Hydrogen ZSM-5/ beta nuclear shell-shaped molecular sieve catalyzer HZB-Cat3 are 50.6%; 1,3, the 5 trimethylbenzene transformation efficiencys of modified ZSM-5/beta nuclear shell-shaped molecular sieve catalyzer MZB-Cat3 are 56.2%.
[embodiment 1]
5 gram PDDA (20%wt) are dissolved in 495 ml deionized water and stir, the 320 former powder of gram ZSM-5 add in this surface modification agent solution, be warmed up to 30 ℃ and kept 3 hours under whipped state, filter and join in the nanocrystalline suspension of β zeolite after drying in 100 ℃ of air atmospheres and sticked in advance 120 minutes, filter and namely get after drying the rear ZSM-5 powder of processing in 100 ℃ of air atmospheres.Can obtain the beta-zeolite molecular sieve synthetic system after 40 gram tetraethyl orthosilicates, 8 gram sodium aluminates, 18 gram sodium-chlor, 6 milliliters of sulfuric acid, 20 milliliters of tetraethyl ammonium hydroxides, 10 milliliters of ammoniacal liquor and the even plastic of 400 ml waters.Add 320 grams process rear ZSM-5 powder and stirred 2 hours in becoming glue.This mixed system moves in teflon-lined stainless steel crystallizing kettle, and in 140 ℃ of baking ovens, static crystallization got final product in 72 hours.The XRD figure spectrum of gained sample has the characteristic diffraction peak of ZSM-5 and beta-zeolite molecular sieve simultaneously.By the SEM spectrogram as seen, at the ZSM-5 outside surface, the fine particle that evenly distributes, the shell coverage is 90%, and the diameter of these fine particles is about 100 nanometers, and the fine particle of β zeolite forms continuous shell at the outside surface of ZSM-5.This just can confirm that the gained molecular screen material is the core-shell type zeolite molecular sieve of β zeolite polycrystalline particle parcel ZSM-5 crystal grain.SiO through the β zeolite of the outside surface of this core-shell type molecular sieve of XPS analysis
2/ Al
2O
3Mol ratio is 80, is designated as core-shell molecular sieve CS1.
Gained core-shell type molecular sieve product C S1 in 550 ℃ (3 ℃/min) lower roasting 6h is with removed template method, use 20% ammonium chloride solution in 95 ℃ again, by dry after liquid-solid ratio 4: 1 exchange 4 hours, suction filtration, washing, repetition 4 times, take 20 gram desciccates, 17 gram aluminum oxide, 1 milliliter of concentrated nitric acid, 0.3 gram sesbania powder and 17 ml waters, mixing is mediated, extruded moulding, dry under 100 ℃ of conditions, in 550 ℃ of air atmospheres, roasting obtained catalyzer HCS-Cat1 in 4 hours.
Take 20 gram desciccates, 17 gram aluminum oxide, 1 milliliter of concentrated nitric acid, 2.5 gram ammonium molybdates, 0.3 gram sesbania powder and 17 ml waters, mixing is mediated, and extruded moulding is dried under 100 ℃ of conditions, and in 550 ℃ of air atmospheres, roasting obtained catalyzer MCS-Cat1 in 4 hours.
Carry out the active investigation of 1,3,5 trimethylbenzene catalytic cracking reactions on the fixed bed reaction evaluating apparatus.Loaded catalyst is 3.0 grams, and weight space velocity is 1.0 hours
-1, temperature of reaction is 300 ℃, reaction pressure 0.2 MPa, and hydrogen hydrocarbon mol ratio is 6.0.Reaction result can be calculated: 1,3, the 5 trimethylbenzene transformation efficiencys of Hydrogen ZSM-5/ beta nuclear shell-shaped molecular sieve catalyzer HCS-Cat1 are 80.5%; 1,3, the 5 trimethylbenzene transformation efficiencys of modified ZSM-5/beta nuclear shell-shaped molecular sieve catalyzer MCS-Cat1 are 92.8%.
[embodiment 2～7]
Embodiment 2～7th, and with synthetic ratio and the synthesis condition of table 1,1 similar approach and step are synthetic obtains core-shell molecular sieve CS2～7 by implementing, and sees table 1 for details.
Table 1 core-shell molecular sieve preparation condition
[embodiment 8～19]
Embodiment 8～19th, are prepared into Hydrogen core-shell molecular sieve catalyzer HCS-Cat8～13 and modified core shell type molecular sieve catalyst MCS-Cat8～19 according to the similar method of embodiment 1.
The preparation condition of table 2 Hydrogen core-shell molecular sieve catalyzer
| The embodiment numbering | The core-shell molecular sieve catalyzer | The core-shell molecular sieve numbering | Binding agent | Molecular sieve: binding agent, ratio % |
| Embodiment 8 | HCS-Cat8 | CS2 | Al 2O 3 | 95∶5 |
| Embodiment 9 | HCS-Cat9 | CS3 | Al 2O 3 | 60∶40 |
| Embodiment 10 | HCS-Cat10 | CS4 | Al 2O 3 | 45∶55 |
| Embodiment 11 | HCS-Cat11 | CS5 | Al 2O 3 | 70∶30 |
| Embodiment 12 | HCS-Cat12 | CS6 | SiO 2 | 5∶95 |
| Embodiment 13 | HCS-Cat13 | CS7 | SiO 2 | 50∶50 |
The preparation condition of table 3 modified core shell molecular sieve catalyst
| The embodiment numbering | The catalyzer numbering | Molecular screen material | Binding agent | Molecular sieve: binding agent, ratio % | Metal-salt and content, M% |
| Embodiment 8 | MCS-Cat8 | CS2 | Gama-alumina | 95∶5 | Molybdenum oxide, 5% |
| Embodiment 9 | MCS-Cat9 | CS3 | Gama-alumina | 60∶40 | Magnesium chloride, 4% |
| Embodiment 10 | MCS-Cat10 | CS4 | Gama-alumina | 45∶55 | Platinic chloride, 0.3% |
| Embodiment 11 | MCS-Cat11 | CS5 | Gama-alumina | 70∶30 | Magnesium acetate, 9% |
| Embodiment 12 | MCS-Cat12 | CS6 | Silicon sol | 5∶95 | Ammonium molybdate, 15% |
| Embodiment 13 | MCS-Cat13 | CS7 | Silicon sol | 50∶50 | Ammonium chloroplatinate, 0.05% |
| Embodiment 14 | MCS-Cat14 | CS2 | Gama-alumina | 70∶30 | Platinic chloride, 0.05%+magnesium acetate, 4% |
| Embodiment 15 | MCS-Cat15 | CS3 | Gama-alumina | 60∶40 | Ammonium chloroplatinate, 0.01%+ammonium molybdate, 20% |
| Embodiment 16 | MCS-Cat16 | CS4 | Silicon sol | 45∶55 | Magnesium acetate, 9% |
| Embodiment 17 | MCS-Cat17 | CS5 | Silicon sol | 85∶15 | Ammonium molybdate, 20% |
| Embodiment 18 | MCS-Cat18 | CS6 | Silicon sol | 70∶30 | Ammonium chloroplatinate, 0.05% |
| Embodiment 19 | MCS-Cat19 | CS7 | Gama-alumina | 60∶40 | Molybdenum oxide, 30% |
[embodiment 20～25]
Catalyzer HZB-Cat3, MZB-Cat3, HCS-Cat1, MCS-Cat1, HCS-Cat8～11 and MCS-Cat8～11 that comparative example 3, embodiment 1, embodiment 8～11 are made, carry out 1 on the fixed bed reaction evaluating apparatus, 3,5 trimethylbenzene catalytic cracking reactions are active to be investigated, and specifically sees Table 4.Loaded catalyst is 3.0 grams, and weight space velocity is 1.0 hours
-1, temperature of reaction is 300 ℃, reaction pressure 0.2 MPa, and hydrogen hydrocarbon mol ratio is 6.0.Reaction result is as follows:
1,3 of table 4 core-shell molecular sieve, 5-trimethylbenzene reactivity worth
| Comparative example/embodiment numbering | The catalyzer numbering | 1,3,5-trimethylbenzene transformation efficiency, wt% |
| Embodiment 20 | HZB-Cat3 | 50.6 |
| Embodiment 20 | MZB-Cat3 | 56.2 |
| Embodiment 21 | HCS-Cat1 | 80.5 |
| Embodiment 21 | MCS-Cat1 | 92.8 |
| Embodiment 22 | HCS-Cat8 | 70.6 |
| Embodiment 23 | HCS-Cat9 | 82.1 |
| Embodiment 24 | HCS-Cat10 | 76.3 |
| Embodiment 25 | HCS-Cat11 | 89.5 |
| Embodiment 22 | MCS-Cat8 | 78.4 |
| Embodiment 23 | MCS-Cat9 | 83.4 |
| Embodiment 24 | MCS-Cat10 | 81.3 |
| Embodiment 25 | MCS-Cat11 | 90.6 |
[embodiment 26～28]
With catalyzer HZB-Cat1, MZB-Cat1, HCS-Cat12～13 and MCS-Cat12～13 that comparative example 1, embodiment 12～13 make, carry out the active investigation of 1,2,4 trimethylbenzene catalytic cracking reactions on the fixed bed reaction evaluating apparatus, specifically see Table 5.Loaded catalyst is 3.0 grams, and weight space velocity is 1.0 hours
-1, temperature of reaction is 420 ℃, reaction pressure 0.5 MPa, and hydrogen hydrocarbon mol ratio is 6.0.Reaction result is as follows:
1,2 of table 5 core-shell molecular sieve, 4-trimethylbenzene reactivity worth
| Comparative example/embodiment numbering | The catalyzer numbering | 1,2,4-trimethylbenzene transformation efficiency, wt% |
| Embodiment 26 | HZB-Cat1 | 40.0 |
| Embodiment 26 | MZB-Cat1 | 48.3 |
| Embodiment 27 | HCS-Cat12 | 60.6 |
| Embodiment 28 | HCS-Cat13 | 65.3 |
| Embodiment 27 | MCS-Cat12 | 70.3 |
| Embodiment 28 | MCS-Cat13 | 75.2 |
[embodiment 29～30]
With catalyzer HZB-Cat2, MZB-Cat2, HCS-Cat19～20 and MCS-Cat19～20 that comparative example 2, embodiment 19～20 make, carry out the active investigation of 1,2,3 trimethylbenzene catalytic cracking reactions on the fixed bed reaction evaluating apparatus, specifically see Table 6.Loaded catalyst is 3.0 grams, and weight space velocity is 3.0 hours
-1, temperature of reaction is 550 ℃, reaction pressure 3.0 MPas, and hydrogen hydrocarbon mol ratio is 1.0.Reaction result is as follows:
The 1，2，3-trimethylbenzene reactivity worth of table 6 core-shell molecular sieve
| Comparative example/embodiment numbering | The catalyzer numbering | The 1，2，3-trimethylbenzene transformation efficiency, wt% |
| Embodiment 29 | HZB-Cat2 | 88.9 |
| Embodiment 29 | MZB-Cat2 | 89.2 |
| Embodiment 30 | HCS-Cat19 | 95.6 |
| Embodiment 30 | MCS-Cat20 | 99.6 |
Claims (8)
1. the method for a trimethylbenzene catalytic conversion, take trimethylbenzene as raw material, be 300～550 ℃ in temperature of reaction, and reaction pressure is 0.2～3 MPa, and air speed is 1.0～8.0 hours
-1, under the condition of hydrogen/hydrocarbon mol ratio 1～8: 1, raw material contacts with catalyzer, and product generates toluene, dimethylbenzene and durene, and catalyzer used comprises following component in parts by weight:
A) the ZSM-5/ beta nuclear shell-shaped molecular sieve material of 5～95 parts;
B) binding agent of 95～5 parts;
Wherein the nuclear phase of core-shell type molecular sieve is ZSM-5, and shell is that coverage is 50～100% β zeolite grain;
Comprise also that in parts by weight 0.01～30 part is selected from least a metal or the oxide compound that contains in magnesium, molybdenum or platinum in catalyzer;
The synthetic method of described ZSM-5/ beta nuclear shell-shaped molecular sieve comprises the following steps:
A) concentration expressed in percentage by weight that the ZSM-5 zeolite of aequum is joined aequum under 20～95 ℃ is in 0.1～10% cationoid reagent solution, after filtering ZSM-5 zeolite I; The concentration expressed in percentage by weight of ZSM-5 zeolite I being put into aequum under 20～95 ℃ is in 0.1～10% β particle solution, after filtration, after drying the mixture I of ZSM-5 zeolite and β zeolite;
B) silicon source, aluminium source and template R are mixed to get the synthetic liquid of alkalescence of pH＞9, mole proportioning of synthetic liquid is: R/SiO
2=0.02～15, H
2O/SiO
2=4～400, SiO
2/ Al
2O
3=30～∞, M
2O/SiO
2=0～3, M is Na or K;
C) synthesize to above-mentioned alkalescence the mixture I that adds (a) step to obtain in liquid, obtain mixed solution I I; Wherein in the add-on of mixture I and synthetic liquid, the mass ratio of contained silicon-dioxide is 0.5～20: 1;
D) with above-mentioned mixed solution I I in 80～200 ℃ of lower crystallization 2.5～240 hours;
E) crystallization finishes by filtration, washing, ammonium exchange, drying, and getting nuclear phase is ZSM-5, and shell is the beta nuclear shell-shaped zeolite molecular sieve of the ZSM-5/ of β zeolite, and wherein the shell coverage is 50～100%;
Wherein in (a) step, cationoid reagent is selected from least a in polymethylmethacrylate, diallyl dimethyl ammoniumchloride pyridine dicarboxylic acid, ammoniacal liquor, ethamine, n-Butyl Amine 99, tetraethyl ammonium hydroxide, TPAOH, tetraethylammonium bromide, 4-propyl bromide, TBAH; (b) in step, the silicon source is selected from least a in water glass, silicon sol, water glass, white carbon black or atlapulgite; The aluminium source is selected from Tai-Ace S 150, sodium aluminate, aluminum isopropylate, aluminum chloride or γ-Al
2O
3In at least a; Template R is selected from least a in Sodium Fluoride, Neutral ammonium fluoride, tetraethyl ammonium hydroxide, tetraethylammonium bromide.
2. the method for a kind of trimethylbenzene catalytic conversion according to claim 1, is characterized in that the raw material trimethylbenzene is 1，2，3-trimethylbenzene, 1,2, at least a in 4-trimethylbenzene or 1,3,5-trimethylbenzene.
3. the method for a kind of trimethylbenzene catalytic conversion according to claim 1 is characterized in that the silica alumina ratio SiO of ZSM-5 nuclear phase in catalyzer
2/ Al
2O
3Be 20～300; The silica alumina ratio SiO of β zeolite shell
2/ Al
2O
3Be 15～∞.
4. the method for a kind of trimethylbenzene catalytic conversion according to claim 1, is characterized in that catalyzer center phase molecule sieve and the weight ratio of shell molecular sieve are 0.2～30: 1.
5. the method for a kind of trimethylbenzene catalytic conversion according to claim 1 is characterized in that binding agent in catalyzer is selected from silicon sol, pseudo-boehmite, aluminum oxide or clay at least a after acid treatment.
6. the method for a kind of trimethylbenzene catalytic conversion according to claim 5, is characterized in that in catalyzer, binding agent is silicon sol or gama-alumina.
7. the method for a kind of trimethylbenzene catalytic conversion according to claim 1, is characterized in that comprising that in parts by weight 0.05～5 part is selected from least a metal or the oxide compound that contains in magnesium, molybdenum or platinum in catalyzer.
8. the method for a kind of trimethylbenzene catalytic conversion according to claim 1, is characterized in that in catalyzer, β zeolite shell coverage is 50%～90%.
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