CN103120950B - Method for preparing catalyst for shape-selective disproportionation of methylbenzene - Google Patents
Method for preparing catalyst for shape-selective disproportionation of methylbenzene Download PDFInfo
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- CN103120950B CN103120950B CN201110369599.2A CN201110369599A CN103120950B CN 103120950 B CN103120950 B CN 103120950B CN 201110369599 A CN201110369599 A CN 201110369599A CN 103120950 B CN103120950 B CN 103120950B
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for preparing a catalyst for shape-selective disproportionation of methylbenzene, and mainly aims to solve the problems that during preparation of the catalyst, organic silicon is modified for a plurality of times and the use level of the organic silicon is high in the prior art. The method comprises the following steps of: adding 20-95% by weight of a ZSM-5 molecular sieve and 5-80% by weight of an adhesive of a catalyst modified precursor into a synthetic molecular sieve crystallization solution for hydrothermal crystallization, wherein the crystallization solution is a solution containing a template agent; carrying out crystallization at 100-200 DEG C, filtering and solidifying to obtain a catalyst modified product; carrying out soaking modification on hydrothermal crystallization product by using an organic silicon compound; and then roasting to obtain the catalyst for the shape-selective disproportionation of methylbenzene. By adopting the method, the problems are well solved, and the method can be used for industrial production of the catalyst for the shape-selective disproportionation of methylbenzene.
Description
Technical field
The present invention relates to a kind of preparation method of toluene selective disproportionation catalyst.
Background technology
Toluene disproportionation process is one of industrial common reaction, and the benzene that toluene conversion can become using value higher by it and dimethylbenzene, wherein xylene products is the equilibrium composition mixture of its three isomers, and the paraxylene had the call only accounts for about 24%.ZSM-5 zeolite forms pore canal system by 10 yuan of oxygen rings, has medium sized aperture and aperture.The aperture feature of ZSM-5 zeolite allows molecular diameter to be that the paraxylene of 0.63 nanometer spreads rapidly, can seriously hinder molecular diameter to be ortho-xylene and the meta-xylene diffusion of 0.69 nanometer simultaneously.In toluene disproportionation process system, there is following relation in the diffusion coefficient of each species in ZSM-5 duct: benzene >=toluene > ethylbenzene ≈ paraxylene > ortho-xylene ≈ meta-xylene, this fact means the possibility of toluene disproportionation process being carried out to shape selection, can obtain the paraxylene content of isomer far away higher than thermodynamical equilibrium concentration in xylene products.Because outer surface acidity position is to the isomerization of the rich contraposition product non-selectivity diffused out in duct, therefore end product is still equilibrium composition.Therefore, the catalyst with higher para-selectivity be expected, modification be carried out to ZSM-5 molecular sieve and is necessary.Need to add in molecular sieve molded process a large amount of bonding agents to make molecular sieve molded then carry out organic-silicon-modified.And the adding of bonding agent, molecular sieve part surface is covered by bonding agent, and making moieties sieve reactant cannot enter, and follow-up organic-silicon-modifiedly also cannot carry out this impact of place to go, causes catalyst activity to reduce.
Propose in document U.S.Patent 5367099 and 5607888 and prepare toluene selective disproportionation catalyst.Its method of modifying selects the macromolecular compound with thermolysis property, molecular sieve outer surface is deposited on by certain method, pass through high-temperature process again, by these macromolecular compound thermal decompositions, be converted into inert coatings, the acid centre of shielding molecular sieve outer surface, also reduces port size simultaneously to a certain extent.Although catalyst prepared by the method reaches the requirement of Selectivity for paraxylene, its catalyst activity is lower.
At United States Patent (USP) 6486373, have employed compound molecule screen method to improve the activity of toluene selective disproportionation catalyst.It is matrix by ZSM-5 molecular sieve, forms the combination of other pore passage structure in its surface, and then carries out shaping, carries out follow-up modification, reaches the requirement of minimizing modification to improve reactivity.But its modification requires to reduce, but owing to defining other sieve particle layer on ZSM-5 molecular sieve surface, synthesis requires high, must be fine and close in the distribution of other zeolite crystal of molecular sieve surface, otherwise improves the requirement of modification on the contrary, and catalyst activity reduces on the contrary.
The object of the invention is to overcome in previous literature in toluene selective disproportionation catalyst preparation, because bonding agent exists, what cause molecular sieve effective rate of utilization to reduce reduces catalyst activity sex chromosome mosaicism.Catalyst after shaping, by adopting after shaping of catalyst, is carried out hydrothermal crystallizing, bonding agent is transformed the molecular sieve that reactant can be made to diffuse through, solve this problem preferably by the present invention.
Summary of the invention
Technical problem to be solved by this invention is in the catalyst preparation process existed in prior art, organic-silicon-modified problem large with organosilicon consumption often.A kind of preparation method of toluene selective disproportionation catalyst is provided, adopts the method to have the advantage of organic-silicon-modified number of times and the minimizing of organosilicon consumption.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows: a kind of preparation method of toluene selective disproportionation catalyst, comprises the following steps:
(a) with its weight percent meter, by shaping for the catalyst precarsor comprising the ZSM-5 molecular sieve of 20 ~ 95% and the binding agent of 5 ~ 80%;
B above-mentioned catalyst precarsor is joined hydrothermal crystallizing in the crystallization liquid containing template by (), crystallization 1 ~ 500 hour at temperature is 100 ~ 200 DEG C, after filtration, obtains catalyst modification body;
C () carries out dipping modification with organo-silicon compound to catalyst modification body, after drying, obtain toluene selective disproportionation catalyst;
Wherein, described organo-silicon compound are or/and the silicone oil of phenyl containing methyl; Template used is at least one in TPAOH, 4-propyl bromide, Tri-n-Propylamine, alkylamine, cyclohexylamine, ammoniacal liquor; Template weight concentration 1 ~ 30% in crystallization liquid, the weight ratio of crystallization liquid and catalyst precarsor is 1 ~ 600.
In technique scheme, in order to transform that binding agent adopts Crystallization of Zeolite liquid composition can be used for synthesis there is the isostructural molecular sieve of MFI, MOR, BEA, MEL.Crystallization of Zeolite liquid template used is at least one in TPAOH, 4-propyl bromide, Tri-n-Propylamine, alkylamine, cyclohexylamine.Template weight concentration 5 ~ 20% in crystallization liquid, the weight ratio of crystallization liquid and solid is 2 ~ 100.Crystallization condition for modification of precursor is temperature 130 ~ 180 DEG C, crystallization time 4 ~ 200 hours.The ZSM-5 molecular sieve SiO that the present invention adopts
2/ Al
2o
3molecular proportion preferable range is 12 ~ 100, SiO
2/ Al
2o
3molecular proportion more preferably scope is 20 ~ 70.Binding agent used in modifying process is silica or oxidation.Crystallization filter after solid after the solid that obtains and organosilicon impregnation drying can 150 ~ 600 DEG C of roastings under containing oxygen or oxygen-free atmosphere.Describedly prepare toluene selective disproportionation catalyst formed body, after above-mentioned preparation process, carry out Selectivity for paraxylene again improve modification, can be used for improving methylbenzene shape-selective disproportionation reaction active.Dipping modification after Crystallizing treatment organosilicon used be containing methyl or and the silicone oil of phenyl, the formation inertial oxide coating after its roasting, can improve methylbenzene shape-selective disproportionation reaction.Organosilicon dipping adopts that normal temperature is the alkane of liquid, aromatic hydrocarbons one or more carry out flooding or direct impregnation for after dissolution with solvents.Be used for synthesizing containing pure silicon dioxide composition pore passage structure crystallization liquid can be used for synthesizing ZSM-5, modenite, beta zeolite etc. formed duct make reactant by material structure.Form silica inert material to improve the selective of reaction owing to have employed organic-silicon-modified then roasting in the modification that this catalyst is follow-up, therefore preferably adopt crystallization ZSM-5-5 under 100 ~ 260 DEG C of hydrothermal conditions.
By adopting after ZSM-5 molecular sieve is shaping, in the catalyst binding agent silica or and aluminium oxide combination by crystallization liquid and formed body under hydrothermal conditions crystallization transform, make to cover in formed body ZSM-5 molecular sieve surface hinder silica that reactant passes through or and aluminium oxide combination be converted into the combination with duct that reactant can be made to pass through, also solve in catalyst preparation process, bonding agent Partial Blocking molecular sieve pore passage, causes the problem that molecular sieve effective rate of utilization reduces.
When toluene selective disproportionation catalyst formed body crystallization, due in sieve synthesis procedure, bonding agent is solid shape, need template directly in conjunction with the effect of competence exertion template, and when if template molecule is larger, cannot continue after template consumption needed for crystallization to draw from solution, therefore the present invention first carries out crystallization to save the consumption of template again by after first dipping or the continuation dryings such as template.In crystallization liquid and formed body crystallization under hydrothermal conditions, the bonding agent of molecular sieve surface is converted into the duct that reactant can be made to pass through.Longer owing to bonding agent to be all converted into the bond time with pore passage structure in crystallization process, therefore can partly or entirely be converted into reactant by the composition with pore passage structure, to reduce generated time, molecular sieve is not containing binding agent, machine Si modification number of times and organosilicon consumption reduce, and catalyst keeps higher activity, for toluene disproportionation process, Selectivity for paraxylene reaches more than 96%, achieves good technique effect.
Below by specific embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Be the ZSM-5 molecular sieve of 25 and the formed body 100g of 20% weight silica by silicon-aluminum containing molecular proportion, at TPAOH 10g, water 150g, with 1M sulphur acid for adjusting pH to 11.5, crystallization 50 hours under temperature 130 DEG C of hydrothermal conditions, rear filtration washing, then at drying and roasting 150 DEG C 3 hours, obtains modified molecular sieve combination A.Then adopt DC550 silicone oil hexane solution (weight concentration 40%) and solid-to-liquid ratio 1.0 to flood after 2 hours to filter, at 150 DEG C, drying 3 hours, in air atmosphere, little 600 DEG C of roastings 2, repeats once to obtain catalyst B.
[embodiment 2]
Be the ZSM-5 molecular sieve of 13 and the formed body 100g of 60% weight silica by silicon-aluminum containing molecular proportion, at 4-propyl bromide 20g, use water-soluble solution, add ammoniacal liquor 40g (weight concentration 15%), with 1M sulphur acid for adjusting pH to 11.5, share water 300g (weight concentration 15%), thermostatic crystallization 2 hours under temperature 100 DEG C of hydrothermal conditions, then temperature 200 DEG C of constant temperature 20 hours are risen to, rear cooling filtration washing, then at 450 DEG C dry 6 hours, modified molecular sieve combination is obtained.Then adopt methyl-silicone oil trimethylbenzene solution (weight concentration 40%) and solid-to-liquid ratio 10 to flood after 0.5 hour to filter, drying 3 hours at 150 DEG C, in air atmosphere, little 600 DEG C of roastings 2, repeated impregnations roasting secondary obtains catalyst C.
[embodiment 3]
Be the ZSM-5 molecular sieve of 99 and the formed body 100g of 80% weight silica by silicon-aluminum containing molecular proportion, at cyclohexylamine 15g, with 1M sulphur acid for adjusting pH to 11.5, share water 150g, crystallization 70 hours under temperature 120 DEG C of hydrothermal conditions, rear filtration washing, rear cooling filtration washing, then at 500 DEG C dry 3 hours, modified molecular sieve combination is obtained.Then get 10.0g combination adopts 275 silicone oil toluene solutions (weight concentration 1%) and solid-to-liquid ratio 600 to flood filtration after 0.5 hour, drying 3 hours at 150 DEG C, in a nitrogen atmosphere, little 400 DEG C of roastings 9, above-mentioned impregnation-calcination obtains catalyst D totally 6 times.
[embodiment 4]
Be the ZSM-5 molecular sieve of 50 and the formed body 5g of 5% weight silica by silicon-aluminum containing molecular proportion, at TPAOH 80.0g, with 1M sulphur acid for adjusting pH to 11.5, water 3000.0g altogether, crystallization 200 hours under temperature 100 DEG C of hydrothermal conditions, rear filtration washing, then under 450 DEG C of air dry 3 hours, obtains modified molecular sieve combination.Then then get 10.0g combination adopts 275 silicone oil n-undecane solution (weight concentration 30%) and solid-to-liquid ratio 0.1 to flood after 0.5 hour at nitrogen 150 DEG C dry 3 hours, under rare air atmosphere (10% oxygen content), 400 DEG C of roastings 9 hours, impregnation-calcination obtained catalyst E.
[embodiment 5]
Be the ZSM-5 molecular sieve of 30 and the formed body 100g of 15% weight silica by silicon-aluminum containing molecular proportion, at ethamine content 5%, n-propylamine content 1%, adopt with 1M sulphur acid for adjusting pH to 11.5, moisture 150g altogether, crystallization 60 hours under temperature 160 DEG C of hydrothermal conditions, rear filtration washing, then under 300 DEG C of air dry 3 hours, modified molecular sieve combination is obtained.Then then get 10.0g combination adopts 275 silicone oil and solid-to-liquid ratio 0.9 to flood filtration after 3 hours, drying 6 hours at nitrogen 150 DEG C, under rare air atmosphere (5% oxygen content), 550 DEG C of roastings 5 hours, above-mentioned impregnation-calcination altogether secondary obtains catalyst F.
[embodiment 6]
Be the ZSM-5 molecular sieve of 20 and the formed body 100g of 15% weight silica and 3% re-oxidation aluminium by silicon-aluminum containing molecular proportion, at tetraethyl ammonium hydroxide 12g, water 150g, with 1M sulphur acid for adjusting pH to 12, moisture 400g altogether, crystallization 20 hours under temperature 160 DEG C of hydrothermal conditions, rear filtration washing, then drying and roasting 3 hours under 450 DEG C of air, obtains modified molecular sieve combination.Then then get 10.0g combination adopts 277 silicone oil and solid-to-liquid ratio 5 to flood after 3 hours at nitrogen 150 DEG C dry 6 hours, and under rare air atmosphere (15% oxygen content), 550 DEG C of roastings 5 hours, above-mentioned impregnation-calcination obtains catalyst G totally three times.
[embodiment 7]
Be the ZSM-5 molecular sieve of 70 and the formed body 100g of 15% weight silica and 1% re-oxidation aluminium by silicon-aluminum containing molecular proportion, at tetraethyl ammonium hydroxide 20g, ammonium fluoride 1.0g, be dissolved in water, with 1M sulphur acid for adjusting pH to 12, moisture 400g altogether, crystallization 20 hours under temperature 160 DEG C of hydrothermal conditions, rear filtration washing, then drying and roasting 3 hours under 450 DEG C of air, obtains modified molecular sieve combination.Then then get 10.0g combination adopts 277 silicone oil and solid-to-liquid ratio 5 to flood after 3 hours at nitrogen 150 DEG C dry 6 hours, and under air, 500 DEG C of roastings 5 hours, above-mentioned impregnation-calcination once obtained catalyst H altogether.
[embodiment 8]
Be the ZSM-5 molecular sieve of 40 and the formed body 100g of 15% weight silica and 10% re-oxidation aluminium by silicon-aluminum containing molecular proportion, at 20 DEG C of saturated ammoniacal liquor 15g, be diluted with water, with 1M sulphur acid for adjusting pH to 12, moisture 400g altogether, crystallization 4 hours under temperature 200 DEG C of hydrothermal conditions, rear filtration washing, then drying and roasting 3 hours under 200 DEG C of air, obtains modified molecular sieve combination.Then then get 10.0g combination adopts methyl-silicone oil and solid-to-liquid ratio 20 to flood after 3 hours at nitrogen 150 DEG C dry 6 hours, and under rare air atmosphere (15% oxygen content), 550 DEG C of roastings 5 hours, above-mentioned impregnation-calcination obtains catalyst I totally three times.
[embodiment 9]
By catalyst obtained for embodiment 1 ~ 8, fixed bed reaction evaluating apparatus carries out the investigation of toluene disproportionation process activity and selectivity.Loaded catalyst is 5.0 grams, and weight space velocity is 4.0h
-1, reaction temperature is 420 DEG C, and reaction pressure is 2.8MPa, and hydrogen hydrocarbon mol ratio is 2.Reaction result lists in table 1.Wherein:
Toluene conversion=(entering the weight of the weight one reactor outlet toluene of reactor toluene)/(entering the weight of reactor toluene) * 100%
Paraxylene para-selectivity=(in product paraxylene mass percent)/(in product xylene mass percentage) * 100%
Table 1
| Catalyst | Toluene conversion % | Paraxylene para-selectivity % |
| A | 50.8 | 24.1 |
| B | 33.7 | 93.8 |
| C | 31.6 | 85％ |
| D | 15.0 | 96.2 |
| E | 24.1 | 93.9 |
| F | 33.5 | 93.4 |
| G | 28.1 | 82.3 |
| H | 25.2 | 80.9 |
| I | 33.2 | 78.9 |
[comparative example 1]
Be the ZSM-5 molecular sieve of 25 and the formed body X100g of 20% weight silica by silicon-aluminum containing molecular proportion, then adopt DC550 silicone oil to flood three times and obtain catalyst Y.Identical with above-described embodiment appreciation condition, evaluation result is in table 2.
Table 2
| Catalyst | Toluene conversion % | Paraxylene para-selectivity % |
| X | 50.8 | 24.1 |
| Y | 30.2 | 90.1 |
Claims (6)
1. a preparation method for toluene selective disproportionation catalyst, comprises the following steps:
(a) with its weight percent meter, by shaping for the catalyst precarsor comprising the ZSM-5 molecular sieve of 20 ~ 95% and the binding agent of 5 ~ 80%;
B above-mentioned catalyst precarsor is joined hydrothermal crystallizing in the crystallization liquid containing template by (), crystallization 1 ~ 500 hour at temperature is 100 ~ 200 DEG C, after filtration, obtains catalyst modification body;
C () carries out dipping modification with organo-silicon compound to catalyst modification body, after drying, obtain toluene selective disproportionation catalyst;
Wherein, described binding agent is at least one in silica or aluminium oxide; The SiO of described ZSM-5 molecular sieve
2/ Al
2o
3molecular proportion is 12 ~ 100; Template weight concentration 5 ~ 20% in crystallization liquid; Described organo-silicon compound are or/and the silicone oil of phenyl containing methyl; Template used is at least one in TPAOH, 4-propyl bromide, Tri-n-Propylamine, alkylamine, cyclohexylamine, ammoniacal liquor; Described Crystallization of Zeolite liquid is the crystallization liquid for synthesizing the molecular sieve with MFI, MOR, BEA, MEL structure, and wherein the mol ratio of each material is SiO
2: Al
2o
3: H
2o=a:1:b, wherein the span of a is the span of 1 ~ 100, b is 5 ~ 6000; Template weight concentration 1 ~ 30% in crystallization liquid, the weight ratio of crystallization liquid and catalyst precarsor is 2 ~ 100.
2. the preparation method of toluene selective disproportionation catalyst according to claim 1, is characterized in that crystallization liquid is the Crystallization of Zeolite liquid of synthesis MFI type structure.
3. the preparation method of toluene selective disproportionation catalyst according to claim 1, is characterized in that (c) step repeats 1 ~ 6 time.
4. the preparation method of toluene selective disproportionation catalyst according to claim 1, is characterized in that (b) step crystallization temperature 130 ~ 180 DEG C, crystallization time 4 ~ 200 hours.
5. the preparation method of toluene selective disproportionation catalyst according to claim 1, is characterized in that the catalyst modification body roasting at 150 ~ 600 DEG C obtained after crystallization in (b) step; Dried solid roasting at 150 ~ 600 DEG C in (c) step.
6. the preparation method of toluene selective disproportionation catalyst according to claim 1, it is characterized in that organosilicon dipping adopts that normal temperature is the alkane of liquid, at least one in aromatic hydrocarbons is solvent, dipping or direct impregnation after dissolving, solution usage is solvent and solute weight ratio 0.1 ~ 100.
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| CN112844454A (en) * | 2019-11-12 | 2021-05-28 | 惠生工程（中国）有限公司 | ZSM-5 catalyst and preparation method and application thereof |
| CN112844453B (en) * | 2019-11-12 | 2023-07-28 | 惠生工程（中国）有限公司 | ZSM-5 catalyst and preparation method and application thereof |
| CN114425407B (en) * | 2020-10-10 | 2024-01-30 | 中国石油化工股份有限公司 | Modification method of molecular sieve catalyst for toluene methanol shape-selective methylation reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5367099A (en) * | 1993-05-28 | 1994-11-22 | Mobil Oil Corp. | Selective toluene disproportionation process (STDP) with ex situ selectivated zeolite catalyst |
| CN1765499A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Preparation method of toluene selective disproportionation catalyst |
| CN101121140A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing catalyst for methylbenzene shape selective disproportionation reaction to synthesizing para-xylene |
| CN101722035A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Catalyst with shape selecting function |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101098495B1 (en) * | 2005-08-15 | 2011-12-26 | 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙 | - Process for the manufacture of catalysts used for producing para-xylene by toluene shape selective alkylation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5367099A (en) * | 1993-05-28 | 1994-11-22 | Mobil Oil Corp. | Selective toluene disproportionation process (STDP) with ex situ selectivated zeolite catalyst |
| CN1765499A (en) * | 2004-10-29 | 2006-05-03 | 中国石油化工股份有限公司 | Preparation method of toluene selective disproportionation catalyst |
| CN101121140A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for preparing catalyst for methylbenzene shape selective disproportionation reaction to synthesizing para-xylene |
| CN101722035A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Catalyst with shape selecting function |
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