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CN102861607A - EU-1/ZSM-5 composite molecular sieve, preparation method of EU-1/ZSM-5 composite molecular sieve and application of EU-1/ZSM-5 composite molecular sieve - Google Patents

EU-1/ZSM-5 composite molecular sieve, preparation method of EU-1/ZSM-5 composite molecular sieve and application of EU-1/ZSM-5 composite molecular sieve Download PDF

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Publication number
CN102861607A
CN102861607A CN2011101884311A CN201110188431A CN102861607A CN 102861607 A CN102861607 A CN 102861607A CN 2011101884311 A CN2011101884311 A CN 2011101884311A CN 201110188431 A CN201110188431 A CN 201110188431A CN 102861607 A CN102861607 A CN 102861607A
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molecular sieve
zsm
composite molecular
crystallization
composite
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张志智
秦波
刘全杰
张喜文
凌凤香
孙万富
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention provides an EU-1/ZSM-5 composite molecular sieve, a preparation method of the EU-1/ZSM-5 composite molecular sieve and application of the EU-1/ZSM-5 composite molecular sieve. A ZSM-5 molecular sieve in the EU-1/ZSM-5 composite molecular sieve is inlaid at the periphery of an EU-1 molecular sieve, a weight content of the EU-1 molecular sieve in the composite molecular sieve is 30%-70%, a sialsphere molar ratio of the composite molecular sieve is 30-50, a mesoporous volume of the composite molecular sieve is 30%-75% of total pore volume, and a mesoporous pore diameter concentrates upon 30-50nm. The preparation method of the EU-1/ZSM-5 composite molecular sieve comprises a crystallization material preparation process, a crystallization process, and filtering, washing, drying and roasting processes after the crystallization process. The EU-1/ZSM-5 composite molecular sieve is applied to C8 aromatic hydrocarbon isomerization reaction, wherein application conditions are that the temperature is 350-420 DEG C, the reaction pressure is 0.6-1.1MPa, the hydrogen hydrocarbon molar ratio is 3-5, and the raw material quality airspeed is 3.0-6.0h<-1>. The composite molecular sieve has two molecular sieve crystalline phases, and has a hole channel with a big hole diameter, so that a problem that catalysis performance is influenced by low spread efficiency in the application of a micropore molecular sieve can be solved.

Description

A kind of EU-1/ZSM-5 composite molecular screen and its preparation method and application
Technical field
The present invention relates to a kind of EU-1/ZSM-5 composite molecular screen and its preparation method and application.
Background technology
The EU-1 molecular sieve is a kind of mesopore high-silica zeolite, has the netted micropore canals structure of one dimension, (orifice diameter is 0.58 * 0.41nm) and twelve-ring side pocket (being of a size of 0.68 * 0.58 * 0.81 nm) structure of vertical UNICOM with it to contain the straight-through duct of ten-ring, be a class has characteristics very much on pore passage structure molecular sieve, they are synthetic a lot of with application study.French national oil research institute in 1998 the synthetic of EUO topological structure molecular sieve that begin one's study, it is applied to xylene isomerization catalyst as acid constituent element, adopting EUO topological structure molecular sieve under identical condition is that the catalyst of acid constituent element has higher activity and selectivity, has good prospects for commercial application.Chinese patent CN01121423.6, CN01121442.2 and CN200610112735.9 have embodied the performance of EU-1 molecular sieve on the dimethylbenzene isomery.
ZSM-5 zeolite also is a kind of mesopore high-silica zeolite, it has unique three-dimensional channel structure and acid strength distributes, most apertures have the characteristic of high silica alumina ratio and oleophilic drainage about 0.55 nm, have simultaneously the high characteristics of heat endurance and catalytic activity.Therefore be widely used in the catalytic process such as isomerization, alkylation and aromatisation.US Patent No. 4939110, US4482773 and Chinese patent CN1051871, CN101541419 have embodied the performance of ZSM-5 molecular sieve on the dimethylbenzene isomery.
The above-mentioned EU-1 of showing zeolite and ZSM-5 zeolite all have important purposes at petrochemical industry.Because the characteristics of EU-1 type zeolite molecular sieve and ZSM-5 zeolite molecular sieve, EU-1 type zeolite molecular sieve and ZSM-5 zeolite molecular sieve are combined with each other, both learn from other's strong points to offset one's weaknesses to make it, mutually replenish, synthetic a kind of composite zeolite molecular sieve with dual structure and acidity can be regulated both structure and sour the distribution, better meets the demand of commercial Application.
Summary of the invention
The object of the invention provides a kind of EU-1/ZSM-5 composite molecular screen and its preparation method and application, this composite molecular screen is when having above-mentioned two kinds of molecular sieve crystalline phases, duct with larger aperture can solve diffuser efficiency that micro porous molecular sieve runs into low and affect the problem of catalytic performance in application.
EU-1/ZSM-5 composite molecular screen of the present invention, ZSM-5 molecular sieve is embedded in around the EU-1 molecular sieve in this composite molecular screen, the weight content of EU-1 molecular sieve in composite molecular screen is 30%～70%, the silica alumina ratio of composite molecular screen is 30～50, the mesoporous pore volume of composite molecular screen accounts for 30% ~ 75% of total pore volume, and mesoporous aperture concentrates on 30 ~ 50nm.
The preparation method of EU-1/ZSM-5 composite molecular screen of the present invention comprises filtration after crystallization material process for preparation, crystallization process and the crystallization, washing, drying and roasting process.
The described crystallization material of the inventive method process for preparation fully mixes EU-1 molecular sieve, silicon source, water and template according to a certain ratio, and each component with the ratio of (by its oxide) in silicon source is in the crystallization material:
EU-1/SiO 2(gram/gram)=0.60 ~ 1.59;
R/SiO 2(moles/mole)=0.31 ~ 0.64;
H 2O/SiO 2(moles/mole)=25 ~ 91;
Be preferably:
EU-1/SiO 2(gram/gram)=0.60 ~ 1.86;
R/SiO 2(moles/mole)=0.23 ~ 0.54;
H 2O/SiO 2(moles/mole)=40 ~ 75;
R represents template.
Described template R is the mixture of TPAOH (TPAOH) and 4-propyl bromide (TPABr); The mol ratio of the addition of TPAOH and silicon source (by oxide) is 0.09 ~ 0.20, preferred 0.10 ~ 0.18.Described silicon source can be White Carbon black, Ludox, waterglass, silicic acid or ethyl orthosilicate, preferred Ludox; Described EU-1 molecular sieve is crystal seed, and the EU-1 molecular sieve can be the sodium type molecular sieve of roasting or the molecular sieve of roasting not, is preferably the sodium type EU-1 molecular sieve of roasting.
Crystallization process described in the inventive method is that the crystallization material that will be mixed with places stainless steel still container to carry out static crystallization or the dynamic crystallization of constant temperature, and crystallization temperature is 100 ~ 140 ℃, crystallization time 1 ~ 3d.
EU-1/ZSM-5 composite molecular screen of the present invention is at C 8Application in the aromatics isomerization reaction, application conditions is 350～420 ℃ of temperature; Reaction pressure 0.6～1.1MPa; Hydrogen hydrocarbon mol ratio 3～5; Material quality air speed 3.0～6.0h -1
The EU-1/ZSM-5 composite molecular screen of the present invention's preparation is significantly different from conventional ZSM-5 zeolite and EU-1 molecular sieve.The diffraction maximum at 2 θ=23.1 ± 0.5 places that belongs to ZSM-5 molecular sieve among the present invention significantly weakens.Belong to enlarging markedly in the diffraction maximum at 2 θ=7.5 ± 0.5 places and the diffraction maximum d value at 2 θ=8.1 ± 0.5 places of EU-1 molecular sieve and ZSM-5 molecular sieve, belong to and enlarge markedly also being worth at 2 θ=23 ± 0.5 diffraction maximum d of place at the diffraction maximum at 2 θ=20 ± 0.5 places and ZSM-5 of EU-1 molecular sieve.The EU-1/ZSM-5 composite molecular screen that the inventive method makes all increases at aspects such as acid strength, heat and hydrothermal stabilities.
Contain a large amount of mesopore orbits in the composite molecular screen provided by the present invention, the micropore canals of binding molecule sieve self is in the situation that not by the mesopore molecular sieve template, form Jie's micropore gradient duct.When micro porous molecular sieve is used for catalytic reaction, especially in the situation that reactant molecule intermediate large or that form is larger, micro porous molecular sieve often can not meet the demands, reactant molecule is difficult to contact active sites and reacts, or limited by bulk, large intermediate is difficult to form, and reactivity and life-span are relatively poor.The reaction diffusion restriction has been eliminated in the existence of mesopore orbit, has satisfied reactant or large intermediate to the requirement in catalyst duct, is conducive to efficient, the long-life operation of catalytic reaction.EU-1/ZSM-5 composite molecular screen of the present invention is compared with existing modenite, at C 8Demonstrate high activity in the aromatics isomerization reaction.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the composite molecular screen of the embodiment of the invention 1 preparation.
Fig. 2 is the stereoscan photograph of the composite molecular screen of the embodiment of the invention 1 preparation.
The specific embodiment
Below in conjunction with embodiment the present invention is further detailed.
The present invention carries out phase to the EU-1/ZSM-5 composite molecular screen and measures the D/max-2500 type full-automatic rotating target x-ray diffractometer that the x-ray diffractometer that adopts is the production of Rigaku Co., Ltd..During experiment, sample is ground to the above compressing tablet of 300 orders, the machine of then going up characterizes.Experiment condition: the Cu target, K α radiation source, graphite monochromator, operating voltage 40kV, tube current 80mA, sweep limits is 5-40 o, sweep speed is 8 o/ min, step-length is 0.01 ο
Embodiment 1
In beaker, successively add 7ml TPAOH and 6.4g TPABr, 50ml distilled water, stir, add again 5gEU-1 molecular sieve crystal seed, stir 10min, add at last the 12ml Ludox, the synthesis reactor of packing into behind the stirring 30min.120 ℃ of heating 48h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying namely obtains the EU-1/ZSM-5 composite molecular screen at 550 ℃ of lower roasting 6h.
The XRD spectra of this EU-1/ZSM-5 composite molecular screen and stereoscan photograph are as shown in Figure 1, 2.As can be seen from Figure 1, the characteristic peak of EU-1 molecular sieve and ZSM-5 molecular sieve is quite obvious in this composite molecular screen.As can be seen from Figure 2, the structure of this composite molecular screen is that ZSM-5 molecular sieve closely is embedded in EU-1 molecular sieve composite molecular screen particle on every side.The silica alumina ratio of this composite molecular screen is 38, and EU-1 molecular sieve weight content is 40% in the composite molecular screen, and mesoporous pore volume accounts for 60% of total pore volume, and mesoporous aperture concentrates on 42nm.
Embodiment 2
In beaker, successively add 7ml TPAOH and 3.2g TPABr, 50ml distilled water, stir, add again 5gEU-1 molecular sieve crystal seed, stir 10min, add at last the 12ml Ludox, the synthesis reactor of packing into behind the stirring 30min.140 ℃ of heating 26h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying namely obtains the EU-1/ZSM-5 composite molecular screen at 550 ℃ of lower roasting 6h.
The silica alumina ratio of this composite molecular screen is 38, and EU-1 molecular sieve weight content is 40% in the composite molecular screen, and mesoporous pore volume accounts for 68% of total pore volume, and mesoporous aperture concentrates on 45nm.
Embodiment 3
In beaker, successively add 5ml TPAOH and 6.4g TPABr, 50ml distilled water, stir, add again 5gEU-1 molecular sieve crystal seed, stir 10min, add at last the 12ml Ludox, the synthesis reactor of packing into behind the stirring 30min.130 ℃ of heating 40h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying namely obtains the EU-1/ZSM-5 composite molecular screen at 550 ℃ of lower roasting 6h.
The silica alumina ratio of this composite molecular screen is 39, and EU-1 molecular sieve weight content is 40% in the composite molecular screen, and mesoporous pore volume accounts for 72% of total pore volume, and mesoporous aperture concentrates on 48nm.
Embodiment 4
In beaker, successively add 9ml TPAOH and 6.4g TPABr, 50ml distilled water, stir, add again 5gEU-1 molecular sieve crystal seed, stir 10min, add at last the 12ml Ludox, the synthesis reactor of packing into behind the stirring 30min.135 ℃ of heating 36h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying namely obtains the EU-1/ZSM-5 composite molecular screen at 550 ℃ of lower roasting 6h.
The silica alumina ratio of this composite molecular screen is 42, and EU-1 molecular sieve weight content is 30% in the composite molecular screen, and mesoporous pore volume accounts for 54% of total pore volume, and mesoporous aperture concentrates on 38nm.
Embodiment 5
In beaker, successively add 9ml TPAOH and 6.4g TPABr, 50ml distilled water, stir, add again 5gEU-1 molecular sieve crystal seed, stir 10min, add at last the 12ml Ludox, the synthesis reactor of packing into behind the stirring 30min.125 ℃ of heating 30h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying namely obtains the EU-1/ZSM-5 composite molecular screen at 550 ℃ of lower roasting 6h.
The silica alumina ratio of this composite molecular screen is 40, and EU-1 molecular sieve weight content is 40% in the composite molecular screen, and mesoporous pore volume accounts for 42% of total pore volume, and mesoporous aperture concentrates on 38nm.
Embodiment 6
In beaker, successively add 5ml TPAOH and 6.4g TPABr, 50ml distilled water, stir, add again 5gEU-1 molecular sieve crystal seed, stir 10min, add at last the 12ml Ludox, the synthesis reactor of packing into behind the stirring 30min.110 ℃ of heating 68h filter resulting product in baking oven, are washed with distilled water to neutrality, and drying namely obtains the EU-1/ZSM-5 composite molecular screen at 550 ℃ of lower roasting 6h.
The silica alumina ratio of this composite molecular screen is 40, and EU-1 molecular sieve weight content is 60% in the composite molecular screen, and mesoporous pore volume accounts for 52% of total pore volume, and mesoporous aperture concentrates on 35nm.
Embodiment 7
The embodiment of the invention 1 prepared EU-1/ZSM-5 composite molecular screen is carried out three ammonium exchanges and double roasting with the 1N ammonium nitrate solution under 60 ℃, make hydrogen type molecular sieve.Make binding agent with aluminium oxide, the equi-volume impregnating loaded metal platinum, drying and roasting is made catalyst.Molecular sieve content is 15% in the catalyst, and the platinum load capacity is 1%.Adopt the catalyst C of EU-1/ZSM-5 composite molecular screen of the present invention 8The aromatics isomerization reaction.Table 1 is used C 8The composition of aroamtic hydrocarbon raw material.C 8The aromatics isomerization reaction is exactly the Mixed XYLENE that the meta-xylene in the raw material is become equilibrium concentration with the ethylbenzene isomery.The process conditions of reaction are: reaction temperature 380 oC, reaction pressure 0.72 MPa, C 8Aroamtic hydrocarbon raw material mass space velocity 5.0 h -1, hydrogen hydrocarbon mol ratio 3.7.Reaction result is dimethylbenzene yield 97%; Conversion of ethylbenzene 20%; The ratio that paraxylene accounts for total aromatic hydrocarbons is 23.2, reaches equilibrium concentration.
Table 1 reaction raw materials forms.
Form <C7 Toluene EB PX MX OX
Content, % 3.2 0.13 7.56 0.40 61.88 26.78
 
Comparative example 1(chooses modenite, under the same terms, carries out activity rating)
Modenite is carried out three ammonium exchanges and double roasting with the 1N ammonium nitrate solution under 60 ℃, make hydrogen type molecular sieve.Make binding agent with aluminium oxide, the equi-volume impregnating loaded metal platinum, drying and roasting is made catalyst.Molecular sieve content is 15% in the catalyst, and the platinum load capacity is 1%.The catalyst C of modenite 8The aromatics isomerization reaction.Table 1 is used C 8The composition of aroamtic hydrocarbon raw material.The process conditions of reaction are: reaction temperature 380 oC, reaction pressure 0.72 MPa, C 8Aroamtic hydrocarbon raw material mass space velocity 5.0 h -1, hydrogen hydrocarbon mol ratio 3.7.Reaction result is dimethylbenzene yield 95; Conversion of ethylbenzene 18%; The ratio that paraxylene accounts for total aromatic hydrocarbons is 21.2, does not also reach equilibrium concentration.

Claims (10)

1. EU-1/ZSM-5 composite molecular screen, ZSM-5 molecular sieve is embedded in around the EU-1 molecular sieve in this composite molecular screen, the weight content of EU-1 molecular sieve in composite molecular screen is 30%～70%, the silica alumina ratio of composite molecular screen is 30～50, the mesoporous pore volume of composite molecular screen accounts for 30% ~ 75% of total pore volume, and mesoporous aperture concentrates on 30 ~ 50nm.
2. the preparation method of the described molecular sieve of claim 1 comprises filtration after crystallization material process for preparation, crystallization process and the crystallization, washing, drying and roasting process.
3. method according to claim 2 is characterized in that described crystallization material process for preparation fully mixes EU-1 molecular sieve, silicon source, water and template according to a certain ratio, and each component with the ratio of silicon source (by its oxide) is in the crystallization material:
EU-1/SiO 2(gram/gram)=0.60 ~ 1.59;
R/SiO 2(moles/mole)=0.31 ~ 0.64;
H 2O/SiO 2(moles/mole)=25 ~ 91;
R represents template.
4. according to claim 2 or 3 described methods, it is characterized in that each component in the crystallization material with the ratio of silicon source (by its oxide) is:
EU-1/SiO 2(gram/gram)=0.60 ~ 1.86;
R/SiO 2(moles/mole)=0.23 ~ 0.54;
H 2O/SiO 2(moles/mole)=40 ~ 75.
5. method according to claim 3, it is characterized in that described template R is the mixture of TPAOH (TPAOH) and 4-propyl bromide (TPABr), the mol ratio of the addition of TPAOH and silicon source (by oxide) is 0.09 ~ 0.20.
6. method according to claim 5 is characterized in that the addition of TPAOH and the mol ratio of silicon source (by oxide) are 0.10 ~ 0.18.
7. method according to claim 3 is characterized in that the silicon source is White Carbon black, Ludox, waterglass, silicic acid or ethyl orthosilicate.
8. method according to claim 3 is characterized in that the EU-1 molecular sieve is for through the sodium type molecular sieve of roasting or the molecular sieve of roasting not.
9. method according to claim 2 is characterized in that described crystallization process is static crystallization or the dynamic crystallization of constant temperature, and crystallization temperature is 100 ~ 140 ℃, crystallization time 1 ~ 3d.
10. claim 1 a described molecular sieve is at C 8Application in the aromatics isomerization reaction, concrete application conditions is 350～420 ℃ of reaction temperatures; Reaction pressure 0.6～1.1MPa; Hydrogen hydrocarbon mol ratio 3～5; Material quality air speed 3.0～6.0h -1
CN2011101884311A 2011-07-07 2011-07-07 EU-1/ZSM-5 composite molecular sieve, preparation method of EU-1/ZSM-5 composite molecular sieve and application of EU-1/ZSM-5 composite molecular sieve Pending CN102861607A (en)

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CN104591221A (en) * 2013-11-04 2015-05-06 中国石油化工股份有限公司 SAPO-34/EU-1 composite molecular sieve and synthetic method thereof
CN106669809A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 C8 aromatic hydrocarbon isomerization catalyst, and preparation method and application thereof
CN106946273A (en) * 2016-01-07 2017-07-14 中国石油化工股份有限公司 A kind of EU-1/ZSM-5 composite molecular screens and its synthetic method
CN110694680A (en) * 2019-11-11 2020-01-17 湘潭大学 Catalyst for one-step preparation of 2, 6-dimethylnaphthalene from synthesis gas and 2-methylnaphthalene
CN113165997A (en) * 2018-12-21 2021-07-23 国际壳牌研究有限公司 Isomerization process
CN115672383A (en) * 2022-09-08 2023-02-03 宜昌苏鹏科技有限公司 Preparation method and product of trimethylamine catalyst with high selectivity
CN115959676A (en) * 2021-10-12 2023-04-14 中国科学院大连化学物理研究所 A kind of *MRE molecular sieve and its preparation method and application

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CN104591215A (en) * 2013-11-04 2015-05-06 中国石油化工股份有限公司 EU-1 and Y composite molecular sieve and synthesizing method thereof
CN104591221A (en) * 2013-11-04 2015-05-06 中国石油化工股份有限公司 SAPO-34/EU-1 composite molecular sieve and synthetic method thereof
CN104591221B (en) * 2013-11-04 2016-05-25 中国石油化工股份有限公司 A kind of SAPO-34 and EU-1 composite molecular screen and synthetic method thereof
CN104591215B (en) * 2013-11-04 2016-11-23 中国石油化工股份有限公司 A kind of EU-1 and Y compound molecular sieve and synthetic method thereof
CN106669809A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 C8 aromatic hydrocarbon isomerization catalyst, and preparation method and application thereof
CN106946273A (en) * 2016-01-07 2017-07-14 中国石油化工股份有限公司 A kind of EU-1/ZSM-5 composite molecular screens and its synthetic method
CN113165997A (en) * 2018-12-21 2021-07-23 国际壳牌研究有限公司 Isomerization process
CN110694680A (en) * 2019-11-11 2020-01-17 湘潭大学 Catalyst for one-step preparation of 2, 6-dimethylnaphthalene from synthesis gas and 2-methylnaphthalene
CN115959676A (en) * 2021-10-12 2023-04-14 中国科学院大连化学物理研究所 A kind of *MRE molecular sieve and its preparation method and application
CN115672383A (en) * 2022-09-08 2023-02-03 宜昌苏鹏科技有限公司 Preparation method and product of trimethylamine catalyst with high selectivity
CN115672383B (en) * 2022-09-08 2024-01-26 宜昌苏鹏科技有限公司 Preparation method and product of catalyst for synthesizing trimethylamine with high selectivity

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Application publication date: 20130109