CN101885663A - Method for converting heavy aromatics to light aromatics and transferring alkyl radical - Google Patents
Method for converting heavy aromatics to light aromatics and transferring alkyl radical Download PDFInfo
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- CN101885663A CN101885663A CN2009100572334A CN200910057233A CN101885663A CN 101885663 A CN101885663 A CN 101885663A CN 2009100572334 A CN2009100572334 A CN 2009100572334A CN 200910057233 A CN200910057233 A CN 200910057233A CN 101885663 A CN101885663 A CN 101885663A
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Abstract
The invention relates to a method for converting heavy aromatics to light aromatics and transferring an alkyl radical, which mainly solves the problem of low activity during the reaction of converting the heavy aromatics to the light aromatics and transferring the alkyl radical in the presence of a conventional catalyst. In the invention, a new method for converting the heavy aromatics to the light aromatics and transferring the alkyl radical is adopted, wherein the catalyst comprises the following components in part by weight: a) 5 to 95 parts of nuclear-shell molecular sieve material and b) 95 to 5 parts of adhesive; the nuclear phase of the nuclear-shell molecular sieve is ZSM-5; and the shell layer is beta zeolite grains with coverage of between 50 and 100 percent. The technical scheme solves the problem better and the method can be used in the industrial production of converting the heavy aromatics to the light aromatics and transferring the alkyl radical.
Description
Technical field
The present invention relates to the method for a kind of heavy aromatics lighting and transalkylation.
Background technology
In recent years, heavy aromatics C
9 +A (carbon nine and carbon nine above aromatic hydrocarbons) has become the valuable source of producing light aromatic hydrocarbons, and heavy aromatics takes off the alkyl technology as the important means that improves the heavy aromatics utilization ratio and the adjusting dimethylbenzene equilibrium of supply and demand, more and more causes the concern of Chinese scholars.The heavy aromatics lighting mainly obtains benzene,toluene,xylene etc., can partly relax the PX demand gap.Therefore, the novel process of exploitation heavy aromatics production by lightening xylol, while by-product durene mixture and liquefied gas can make full use of all heavy aromatics resources, satisfies p-Xylol and expands the energy needs, gives full play to C
10The economic benefit of resource.In heavy aromatics lighting and transalkylation reaction, adopt the molecular sieve catalyst desired reaction temperature lower, help avoiding catalyst deactivation.It is several that the domestic and international at present molecular sieve catalyst that uses still is limited to ZSM-5, β zeolite etc. basically.
The strength of acid of ZSM-5 and sour distribution can in very large range be regulated and control.Its crystalline size also can be regulated in the larger context, and the modifiability of structure is big, so ZSM-5 is the molecular screen material that extensively adopts in the research.10 yuan of ring straight channel are of a size of 0.51 * 0.55nm in the ZSM-5 molecular sieve, and passage is of a size of 0.54 * 0.56nm in a zigzag, are usually used in micromolecular cracking reactions such as reaction of intracrystalline shape selective catalysis and gasoline fraction.C
9 +The macromolecular size of A is generally bigger, and as 1,3, the molecular dynamics diameter of 5-tri-isopropyl benzene is 0.95nm, so C
9 +The A macromole transforms major part can carry out on the ZSM-5 surface, and its internal surface acid site utilization ratio is low, so reactive behavior is lower.Owing to easy coking and deactivation in the reaction, catalyst life is also shorter in addition
The β zeolite is up to now to be found unique have intersect the macropore three-dimensional structure supersiliceous zeolite of twelve-ring channel system (12 yuan of ring windows be of a size of 0.76 * 0.64nm), because the singularity of its structure has 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 crucial catalytic material.(Journal of the Japan Petroleum Institute 45:99) also finds the specific activity ZSM-5 height of β zeolite in the conversion reaction of aromatic hydrocarbons macromole to document.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 the β zeolite mechanically mixing because sample strong acidic site comparatively small amt, and external surface area is not high yet, though so reactive behavior than ZSM-5 height, still very low generally.With the ZSM-5 molecular sieve is nuclear phase, and β is nanocrystalline to be 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, [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 the result shows that the coverage of surperficial β shell is very low, only be about 5%, 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 the ZSM-5/ beta nuclear shell-shaped molecular sieve of literature method is 2.5 hours at weight space velocity
-1, temperature of reaction is 440 ℃, and reaction pressure is 3.0 MPas, and hydrogen hydrocarbon mol ratio is that 4.0 o'clock heavy aromatic hydrocarbon light and transalkylation reaction total conversion rate is 41%.
Summary of the invention
Technical problem to be solved by this invention is the active low problem of heavy aromatic hydrocarbon light and transalkylation reaction in the past, and a kind of new heavy aromatics lighting and the method for transalkylation are provided.This method has the high advantage of catalyst activity.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of heavy aromatics lighting and transalkylation, and with C
9 +The A heavy aromatics is a raw material, is 350～500 ℃ in temperature of reaction, and reaction pressure is 0.5～4 MPa, and air speed is 1.0～4.0 hours
-1, under the condition of hydrogen/hydrocarbon mol ratio 1～10: 1, raw material contacts with catalyzer, and product generates toluene, benzene and dimethylbenzene, and used catalyzer comprises following component in parts by weight:
A) 5～95 parts ZSM-5/ beta nuclear shell-shaped molecular sieve material;
B) 95～5 parts binding agent;
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 the technique scheme, β zeolite shell coverage preferable range is 50～90%; 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 the 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 the platinum.
In technique scheme, be used for heavy aromatics lighting and transalkylation reaction Preparation of catalysts method, may further comprise the steps:
A) obtain catalyst Precursors after in the ZSM-5/ of aequum beta nuclear shell-shaped molecular sieve, adding at least a compound kneading that being selected from of the binding agent of aequum and aequum contain in magnesium, molybdenum or the platinum, moulding, drying; 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 the platinum with pickling process with being selected from of aequum, obtain catalyst Precursors after the drying;
B) catalyst Precursors that a) step is obtained carries out roasting under air atmosphere, oxygen-lean atmosphere or oxygen-enriched atmosphere, be warming up to 300～700 ℃ with 0.1～20 ℃/minute speed, kept 0.5～10 hour, and made metallic compound be converted into metal oxide, obtain catalystic material after the cooling.
In technique scheme, the beta nuclear shell-shaped synthesis method of zeolite molecular sieve of ZSM-5/ can be selected from following method preparation, as may further comprise the 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% the cationoid reagent solution, after filtering ZSM-5 zeolite I; ZSM-5 zeolite I is put into aequum under 20 ℃～95 ℃ concentration expressed in percentage by weight is in 0.1～10% the β particle solution, after filtration, after the drying the mixture I of ZSM-5 zeolite and β zeolite;
B) silicon source, aluminium source and template R are mixed the synthetic liquid of the alkalescence that obtains PH＞9, the 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) in the synthetic liquid of above-mentioned alkalescence, add the mixture I that (a) step obtains, obtain mixed solution I I; Wherein the mass ratio of contained silicon-dioxide is 0.5～20: 1 in the add-on of mixture I and the synthetic liquid;
D) with above-mentioned mixed solution I I in 80～200 ℃ of following crystallization 2.5～240 hours;
E) after crystallization finishes after filtration, washing, ammonium exchange, drying, nuclear phase be ZSM-5, shell is the beta nuclear shell-shaped zeolite molecular sieve of the ZSM-5/ of β zeolite, wherein the shell coverage is 50～100%;
Wherein 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, the TBAH in (a) step; (b) the silicon source is selected from least a in water glass, silicon sol, water glass, white carbon black or the atlapulgite in the step; 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, the tetraethylammonium bromide.
The ZSM-5 molecular sieve is because the restriction of pore structure, and internal surface acid site utilization ratio is low and make it at C
9 +Activity is lower in the conversion reaction of A heavy aromatics; Beta-molecular sieve has suitable strength of acid and acid amount, and macroporous structure helps C simultaneously
9 +The diffusion of A heavy aromatics molecule can effectively improve C
9 +A heavy aromatics conversion capability, but use cost is higher; Though the aromatic hydrocarbons activity of conversion of ZSM-5 and β zeolite mechanically mixing sample is still very lower generally than ZSM-5 height; 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 heavy aromatics lighting and transalkylation reaction that the present invention relates to, be the silicon source, prepared the beta nuclear shell-shaped zeolite molecular sieve of ZSM-5/ with at least a in water glass cheap and easy to get, silicon sol, water glass, white carbon black or the atlapulgite with high shell coverage (50～100%), so its C
9 +A heavy aromatics reactive behavior can be improved significantly.In addition, in this Catalysts and its preparation method, also added a certain amount of metal component, active increase has been had promoter action.When adopting catalyzer of the present invention to be used for heavy aromatic hydrocarbon light and transalkylation reaction, what the raw material total conversion rate was higher reaches 65%, has obtained better technical effect.
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 the 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 molecular sieve synthetic system with 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 with after 600 ml waters evenly become glue.This mixed system moves in the teflon-lined stainless steel crystallizing kettle, and static crystallization can obtain zeolite molecular sieve product ZB-1 in 48 hours in 170 ℃ of baking ovens.The XRD figure spectrum of sample has the characteristic diffraction peak of ZSM-5 zeolite molecular sieve, no 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.With the silicon sol is binding agent, and 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.
With the silicon sol is binding agent, and 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.
On the fixed bed reaction evaluating apparatus, carry out heavy aromatic hydrocarbon light and transalkylation reaction performance evaluation.Loaded catalyst is 3.0 grams, and weight space velocity is 4.0 hours
-1, C in the raw material
9A/C
10 +A=80/20, temperature of reaction is 440 ℃, reaction pressure 3.0 MPas, hydrogen hydrocarbon mol ratio is 4.0.Reaction result calculates and can get: the C of Hydrogen ZSM-5 molecular sieve catalyst HZB-Cat1
9 +A transformation efficiency 40.2%, BTX selectivity 56.2%; The C of modified zsm-5 zeolite catalyzer MZB-Cat1
9 +A transformation efficiency 42.3%, BTX selectivity 54.3%.
[comparative example 2]
Comparative example 2 is used for illustrating SiO
2/ Al
2O
3Be preparation and the 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:
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 can obtain the beta-zeolite molecular sieve synthetic system after 600 ml waters evenly become glue, 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.With the aluminum oxide is binding agent, and 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.
With the aluminum oxide is binding agent, 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 are restrained sesbania powder and 17 ml waters, and mixing is mediated, extruded moulding, 540 ℃ of roasting 2h make modified beta molecular sieve catalyzer MZB-Cat2.
On the fixed bed reaction evaluating apparatus, carry out heavy aromatic hydrocarbon light and transalkylation reaction performance evaluation.Loaded catalyst is 3.0 grams, and weight space velocity is 1.0 hours
-1, C in the raw material
9A/C
10 +A=100/0, temperature of reaction is 380 ℃, reaction pressure 1.0 MPas, hydrogen hydrocarbon mol ratio is 4.0.Reaction result calculates and can get: the C of Hydrogen beta-molecular sieve catalyzer HZB-Cat2
9A transformation efficiency 45.6%, BTX selectivity 58.9%; The C of modified beta molecular sieve catalyzer MZB-Cat2
9A transformation efficiency 48.7%, BTX selectivity 61.3%.
[comparative example 3]
Comparative example 3 is used for explanation, with reference to Bouizi etc. at document [Chem.Mater, 18:4959] middle institute reported method, with positive tetraethyl orthosilicate is the synthetic of 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
The positive tetraethyl orthosilicate solution of 211 grams is dissolved in the 200 gram water, is configured to solution A; 407 gram TPAOH solution (concentration 25%) are dissolved in the 100 gram water, are configured to solution B; 104 gram vitriolate of tartar are dissolved in the 240 gram water, are configured to solution C.Solution B is slowly dropped in the solution A, fully stir, add solution C again, the reaction mixture of formation 170 ℃ of crystallization 2 days, obtains the nuclear phase ZSM-5 crystal seed I of big crystal grain.
The positive tetraethyl orthosilicate solution of 5282 grams is dissolved in the 2300 gram water, is configured to solution A; 1326 gram tetraethyl ammonium hydroxide solution (concentration 25%) are dissolved in the 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 0.5wt% deionized water dispersive β again, stick 30min, behind the filtering drying in 540 ℃ (3 ℃/min) down roasting 5h makes the nanometer crystal seed firmly be attached on the ZSM-5 surface, and with this as nuclear crystal seed III.
The positive tetraethyl orthosilicate solution of 5282 grams is dissolved in the 2300 gram water, is configured to solution A; 1326 gram tetraethyl ammonium hydroxide solution (concentration 25%) are dissolved in the 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 nuclear 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) down roasting 6h 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.With the aluminum oxide is 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.
With the aluminum oxide is binding agent, 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 are restrained sesbania powder and 17 ml waters, and mixing is mediated, extruded moulding, 540 ℃ of roasting 2h make modified ZSM-5/beta nuclear shell-shaped molecular sieve catalyzer MZB-Cat3.
On the fixed bed reaction evaluating apparatus, carry out heavy aromatic hydrocarbon light and transalkylation reaction performance evaluation.Loaded catalyst is 3.0 grams, and weight space velocity is 2.5 hours
-1, C in the raw material
9A/C
10 +A=0/100, temperature of reaction is 500 ℃, reaction pressure 3.0 MPas, hydrogen hydrocarbon mol ratio is 10.0.Reaction result calculates and can get: the C of Hydrogen ZSM-5/ beta nuclear shell-shaped molecular sieve catalyzer HZB-Cat3
9 +A transformation efficiency 40.2%, BTX selectivity 62.1%; The C of modified ZSM-5/beta nuclear shell-shaped molecular sieve catalyzer MZB-Cat3
9 +A transformation efficiency 41.3%, BTX selectivity 61.3%.
[embodiment 1]
5 gram PDDA (20%wt) are dissolved in 495 ml deionized water and stir, the former powder of 320 gram ZSM-5 adds in this surface modification agent solution, under whipped state, be warmed up to 30 ℃ and kept 3 hours, filter and in 100 ℃ of air atmospheres, join in the nanocrystalline suspension of β zeolite after the drying and sticked in advance 120 minutes, filter and in 100 ℃ of air atmospheres, promptly get after the drying and handle back ZSM-5 powder.The positive tetraethyl orthosilicate of 40 grams, 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 can obtain the beta-zeolite molecular sieve synthetic system after 400 ml waters evenly become glue.Adding 320 grams are handled back ZSM-5 powder and were stirred 2 hours in becoming glue.This mixed system moves in the teflon-lined stainless steel crystallizing kettle, and static crystallization got final product in 72 hours in 140 ℃ of baking ovens.The XRD figure spectrum of gained sample has the characteristic diffraction peak (see figure 1) of ZSM-5 and beta-zeolite molecular sieve simultaneously.By SEM spectrogram visible (seeing accompanying drawing 2), at the ZSM-5 outside surface, the uniform distribution fine particle, the shell coverage is 90%, and the diameter of these fine particles is about 100 nanometers, and the fine particle of β zeolite forms the successive 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) down roasting 6h with removed template method, use 20% ammonium chloride solution in 95 ℃ again, by liquid-solid ratio exchange in 4: 14 hours, suction filtration, washing, 4 after drying of repetition, take by weighing 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, roasting obtained catalyzer HCS-Cat1 in 4 hours in 550 ℃ of air atmospheres.
Take by weighing 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 roasting obtained catalyzer MCS-Cat1 in 4 hours in 550 ℃ of air atmospheres.
On the fixed bed reaction evaluating apparatus, carry out heavy aromatic hydrocarbon light and transalkylation reaction performance evaluation.Loaded catalyst is 3.0 grams, and weight space velocity is 4.0 hours
-1, C in the raw material
9A/C
10 +A=80/20, temperature of reaction is 440 ℃, reaction pressure 3.0 MPas, hydrogen hydrocarbon mol ratio is 4.0.Reaction result calculates and can get: the C of Hydrogen ZSM-5/ beta nuclear shell-shaped molecular sieve catalyzer HCS-Cat1
9 +A transformation efficiency 40.2%, BTX selectivity 56.2%; The C of modified ZSM-5/beta nuclear shell-shaped molecular sieve catalyzer MCS-Cat1
9 +A transformation efficiency 42.3%, BTX selectivity 54.3%.
[embodiment 2～7]
Embodiment 2～7th, and with the synthetic ratio and the synthesis condition of table 1,1 similar approach and step are synthetic to obtain 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 embodiment 1 similar method.
Table 2 Hydrogen core-shell molecular sieve Preparation of catalysts condition
| 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
[embodiment 20～25]
Catalyzer HZB-Cat1, MZB-Cat1, HCS-Cat.1, MCS-Cat1, HCS-Cat8～11 and MCS-Cat8～11 that comparative example 1, embodiment 1, embodiment 8～11 are made, on the fixed bed reaction evaluating apparatus, carry out heavy aromatic hydrocarbon light and transalkylation reaction performance evaluation, the raw material composition sees Table 4, and concrete reaction result sees Table 5.Loaded catalyst is 3.0 grams, and weight space velocity is 4.0 hours
-1, C in the raw material
9A/C
10 +A=80/20, temperature of reaction is 440 ℃, reaction pressure 3.0 MPas, hydrogen hydrocarbon mol ratio is 4.0.Specific as follows:
Table 4 heavy aromatic hydrocarbon light and transalkylation reaction raw material are formed, wt%
| Title | Non-aromatic | Benzene | Toluene | Ethylbenzene | Dimethylbenzene | Indane | ??C 9A | ??C 10 +A |
| Content | ??0.04 | ??0.02 | ??0.00 | ??0.00 | ??0.03 | ??1.57 | ??79.24 | ??19.10 |
The heavy aromatic hydrocarbon light of table 5 core-shell molecular sieve and transalkylation reaction performance
| Comparative example/embodiment numbering | The catalyzer numbering | ??C 9 +The A transformation efficiency, % | The BTX selectivity, % |
| Embodiment 20 | ??HZB-Cat1 | ??40.2 | ??56.2 |
| Embodiment 20 | ??MZB-Cat1 | ??42.3 | ??54.3 |
| Embodiment 21 | ??HCS-Cat1 | ??40.2 | ??56.2 |
| Embodiment 21 | ??MCS-Cat1 | ??42.3 | ??54.3 |
| Comparative example/embodiment numbering | The catalyzer numbering | ??C 9 +The A transformation efficiency, % | The BTX selectivity, % |
| Embodiment 22 | ??HCS-Cat8 | ??53.9 | ??62.3 |
| Embodiment 23 | ??HCS-Cat9 | ??58.2 | ??61.4 |
| Embodiment 24 | ??HCS-Cat10 | ??53.9 | ??62.3 |
| Embodiment 25 | ??HCS-Cat11 | ??58.2 | ??61.4 |
| Embodiment 22 | ??MCS-Cat8 | ??61.8 | ??62.4 |
| Embodiment 23 | ??MCS-Cat9 | ??63.4 | ??70.2 |
| Embodiment 24 | ??MCS-Cat10 | ??62.4 | ??68.3 |
| Embodiment 25 | ??MCS-Cat11 | ??65.3 | ??67.3 |
[embodiment 26～31]
Catalyzer HZB-Cat1, MZB-Cat1, HCS-Cat12～16 and MCS-Cat12～16 that comparative example 2, embodiment 12～16 are made, carry out heavy aromatic hydrocarbon light and transalkylation reaction performance evaluation on the fixed bed reaction evaluating apparatus, concrete reaction result sees Table 6.Loaded catalyst is 3.0 grams, and weight space velocity is 1.0 hours
-1, C in the raw material
9A/C
10 +A=100/0, temperature of reaction is 380 ℃, reaction pressure 1.0 MPas, hydrogen hydrocarbon mol ratio is 4.0.Specific as follows:
The heavy aromatic hydrocarbon light of table 6 core-shell molecular sieve and transalkylation reaction performance
| Comparative example/embodiment numbering | The catalyzer numbering | ??C 9 +The A transformation efficiency, % | The BTX selectivity, % |
| Embodiment 26 | ??HZB-Cat2 | ??45.6 | ??58.9 |
| Embodiment 26 | ??MZB-Cat2 | ??42.3 | ??54.3 |
| Embodiment 27 | ??HCS-Cat12 | ??53.9 | ??62.3 |
| Embodiment 28 | ??HCS-Cat13 | ??58.2 | ??61.4 |
| Embodiment 29 | ??HCS-Cat14 | ??53.9 | ??62.3 |
| Embodiment 28 | ??HCS-Cat13 | ??58.2 | ??61.4 |
| Embodiment 29 | ??MCS-Cat14 | ??61.8 | ??62.4 |
| Embodiment 30 | ??MCS-Cat15 | ??63.4 | ??70.2 |
| Embodiment 31 | ??MCS-Cat16 | ??65.3 | ??67.3 |
[embodiment 32～35]
With catalyzer HZB-Cat3, MZB-Cat3 and MCS-Cat17～19 that comparative example 3, embodiment 18～20 make, on the fixed bed reaction evaluating apparatus, carry out heavy aromatic hydrocarbon light and transalkylation reaction performance evaluation, concrete reaction result sees Table 7.Loaded catalyst is 3.0 grams, and weight space velocity is 2.5 hours
-1, C in the raw material
9A/C
10 +A=0/100, temperature of reaction is 500 ℃, reaction pressure 3.0 MPas, hydrogen hydrocarbon mol ratio is 10.0.Specific as follows:
The heavy aromatic hydrocarbon light of table 7 core-shell molecular sieve and transalkylation reaction performance
| Comparative example/embodiment numbering | The catalyzer numbering | ??C 9 +The A transformation efficiency, % | The BTX selectivity, % |
| Embodiment 32 | ??HZB-Cat3 | ??40.2 | ?62.1 |
| Embodiment 32 | ??MZB-Cat3 | ??41.3 | ?61.3 |
| Embodiment 33 | ??MCS-Cat17 | ??64.1 | ?60.4 |
| Embodiment 34 | ??MCS-Cat18 | ??52.9 | ?58.3 |
| Embodiment 35 | ??MCS-Cat19 | ??55.3 | ?61.7 |
Claims (8)
1. the method for heavy aromatics lighting and transalkylation is with C
9 +The A heavy aromatics is a raw material, is 350～500 ℃ in temperature of reaction, and reaction pressure is 0.5～4 MPa, and air speed is 1.0～4.0 hours
-1, under the condition of hydrogen/hydrocarbon mol ratio 1～10: 1, raw material contacts with catalyzer, and product generates toluene, benzene and dimethylbenzene, and used catalyzer comprises following component in parts by weight:
A) 5～95 parts ZSM-5/ beta nuclear shell-shaped molecular sieve material;
B) 95～5 parts binding agent;
Wherein the nuclear phase of core-shell type molecular sieve is ZSM-5, and shell is that coverage is 50～100% β zeolite grain.
2. the method for a kind of heavy aromatics lighting according to claim 1 and transalkylation is characterized in that the silica alumina ratio SiO of ZSM-5 nuclear phase in the catalyzer
2/ Al
2O
3Be 20～300; The silica alumina ratio SiO of β zeolite shell
2/ Al
2O
3Be 15～∞.
3. the method for a kind of heavy aromatics lighting according to claim 1 and transalkylation is characterized in that the catalyzer center phase molecule sieve and the weight ratio of shell molecular sieve are 0.2～30: 1.
4. the method for a kind of heavy aromatics lighting according to claim 1 and transalkylation is characterized in that binding agent in the catalyzer is selected from silicon sol, pseudo-boehmite, aluminum oxide or clay at least a after acid treatment.
5. the method for a kind of heavy aromatics lighting according to claim 4 and transalkylation is characterized in that binding agent is silicon sol or gama-alumina in the catalyzer.
6. the method for a kind of heavy aromatics lighting according to claim 1 and transalkylation is characterized in that comprising 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 the platinum in the catalyzer.
7. the method for a kind of heavy aromatics lighting according to claim 6 and transalkylation 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 the platinum in the catalyzer.
8. the method for a kind of heavy aromatics lighting according to claim 1 and transalkylation is characterized in that β zeolite shell coverage is 50～90% in the catalyzer.
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| CN104447159A (en) * | 2014-11-11 | 2015-03-25 | 中国海洋石油总公司 | Combined process method for light conversion of C10<+> heavy aromatics |
| CN109395750A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics adds hydrogen to be saturated light aromatics catalyst processed |
| US10723631B2 (en) | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| US10723630B2 (en) | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| CN111592443A (en) * | 2020-05-29 | 2020-08-28 | 中国海洋石油集团有限公司 | System and method for increasing yield of p-xylene through combination of toluene methylation and heavy aromatic hydrocarbon lightening |
| US10927059B2 (en) | 2018-03-14 | 2021-02-23 | Saudi Arabian Oil Company | Catalyst for converting heavy reformate to produce BTX compounds |
| CN113164936A (en) * | 2018-03-14 | 2021-07-23 | 沙特阿拉伯石油公司 | A metal impregnated ZSM-5+ nanocrystalline zeolite beta composite catalyst; method for converting heavy reformate into BTX by using composite catalyst |
| US11091413B2 (en) | 2018-03-14 | 2021-08-17 | Saudi Arabian Oil Company | Methods of heavy reformate conversion into aromatic compounds |
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| CN104447159A (en) * | 2014-11-11 | 2015-03-25 | 中国海洋石油总公司 | Combined process method for light conversion of C10<+> heavy aromatics |
| CN109395750A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Condensed-nuclei aromatics adds hydrogen to be saturated light aromatics catalyst processed |
| CN109395750B (en) * | 2017-08-18 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for preparing light aromatic hydrocarbon by hydrogenation saturation of polycyclic aromatic hydrocarbon |
| US10723631B2 (en) | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| US10723630B2 (en) | 2018-03-14 | 2020-07-28 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
| US10927059B2 (en) | 2018-03-14 | 2021-02-23 | Saudi Arabian Oil Company | Catalyst for converting heavy reformate to produce BTX compounds |
| CN113164936A (en) * | 2018-03-14 | 2021-07-23 | 沙特阿拉伯石油公司 | A metal impregnated ZSM-5+ nanocrystalline zeolite beta composite catalyst; method for converting heavy reformate into BTX by using composite catalyst |
| US11091413B2 (en) | 2018-03-14 | 2021-08-17 | Saudi Arabian Oil Company | Methods of heavy reformate conversion into aromatic compounds |
| US11472755B2 (en) | 2018-03-14 | 2022-10-18 | Saudi Arabian Oil Company | Methods of heavy reformate conversion into aromatic compounds |
| CN111592443A (en) * | 2020-05-29 | 2020-08-28 | 中国海洋石油集团有限公司 | System and method for increasing yield of p-xylene through combination of toluene methylation and heavy aromatic hydrocarbon lightening |
| CN111592443B (en) * | 2020-05-29 | 2022-07-19 | 中国海洋石油集团有限公司 | System and method for increasing yield of p-xylene through combination of toluene methylation and heavy aromatic hydrocarbon lightening |
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