CN102671694A - Catalyst for selectively preparing paraxylene and method for synthesizing catalyst - Google Patents
Catalyst for selectively preparing paraxylene and method for synthesizing catalyst Download PDFInfo
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Abstract
The invention provides a catalyst for selectively preparing paraxylene, which mainly solves the weaknesses of the catalyst that the reaction activity is low and the selectivity of a target product (paraxylene) is poor. Hydrogen zeolite socony mobile-5 (HZSM-5) zeolite is synthesized through a water-heat synthesizing way, the HZSM-5 zeolite is adopted as a core, and core-shell zeolite silicalite-1/HZSM-5 is synthesized through an in-situ growth method or a secondary growth method. Due to the adoption of the catalyst, the problems that the catalyst activity is low and the target product selectivity is poor can be well solved, the selectivity of the paraxylene is greatly improved, and the activity of the catalyst is reserved.
Description
[technical field]
The present invention relates to the organic synthesis field, be specifically related to catalyst and synthetic method thereof that a kind of selectivity prepares paraxylene.
[background technology]
Paraxylene is very important basic chemical industry raw material, and especially as the raw material of synthetic polyester fibers and plastics and be widely used, and its demand increases day by day.In addition, paraxylene also has purposes very widely in fields such as medicine, agricultural chemicals, fuel and solvents.At present, main xylenes adsorbing separation, toluene and the C of adopting in the industry
9Three kinds of explained hereafter paraxylene of disproportionation and transalkylation and selective disproportionation of toluene.Though selective disproportionation of toluene can obtain the paraxylene of high concentration, the conversion ratio of toluene is low, and has a large amount of accessory substance benzene to generate.And xylene isomerization and toluene and C
9Two kinds of technologies of aromatic disproportion and transalkylation, the concentration of gained paraxylene is merely about 24%, obtain the paraxylene of high concentration; Must adopt very harsh separation condition; And raw material will constantly separate and isomerization with product, and the material treating capacity is big, and production cost is high.
In recent years, to prepare the report of paraxylene a lot of for toluene methylation.(Chemical Reaction Engineering and technology, 2006,22 (4): 305 ~ 309) adopt the CLD method that the HZSM-5 catalyst is carried out modification, though improved the selectivity of paraxylene, the conversion ratio of toluene has only 23.5% to Xie Zaiku etc.(Sinopec publishing house 1990:4-6) adopts alkaline-earth metal that the HZSM-5 catalyst is carried out modification, and the conversion ratio of toluene is higher, but the raising of the selectivity of paraxylene is also not obvious: the selectivity of paraxylene is 44.4% to Ceng Zhaohuai etc. after the Ca modification; The selectivity of paraxylene is merely 38.2% after the Sr modification; And the selectivity of Ba modification gained paraxylene is 38.2%.Guo Xinwen etc. (SCI, 2007,28:922-927) adopting the MCM-22 molecular sieve is catalyst, and adopts its acidity of method modulation of hydrothermal treatment consists, in the methylbenzene methanol methylation reaction, shows certain paraxylene selectivity (42.1%).Li etc. (Catalysis Communications, 2009,10:1609 – 1614) are catalyst with the MCM-22 molecular sieve equally, adopt MgO to carry out modification, and when the load capacity of MgO was 3 wt%, the selectivity of paraxylene was merely 29.4%.When adopting the H-MCM-22/MCM-41 composite molecular screen to be catalyst, in toluene dimethyl carbonate alkylated reaction, show certain paraxylene selectivity equally.Yet when the paraxylene selectivity was 65.3%, the conversion ratio of toluene was merely 10.1%.Can know from above open source literature, obtain simultaneously high activity (high toluene conversion) and high paraxylene optionally catalyst be the difficult point of producing paraxylene.
In the toluene methylation reaction, the HZSM-5 molecular sieve causes the selectivity of paraxylene not high because there is paraxylene isomerization activity site in its surface; And the Silicalite-1 molecular sieve does not have catalytic activity owing to do not possess acidity in the toluene methylation reaction.
[summary of the invention]
The object of the present invention is to provide a kind of is that nuclear, Silicalite-1 molecular sieve are the core-shell type molecular sieve catalyst of shell with the HZSM-5 molecular sieve, and the synthetic method of this catalyst and the application in the preparation paraxylene.
Core-shell molecular sieve Silicalite-1/HZSM-5 catalyst provided by the invention adopts the method for growth in situ or diauxic growth to synthesize.
The synthetic method of core-shell molecular sieve Silicalite-1/HZSM-5 catalyst provided by the invention comprises following steps:
S1 nuclear phase molecular sieve HZSM-5's is synthetic: adopt template through the synthetic SiO of the synthetic method of hydro-thermal
2/ Al
2O
3It is 25 ~ 300 HZSM-5 molecular sieve;
S2 is a nuclear with above-mentioned synthetic HZSM-5 molecular sieve, joins TPAOH/SiO
2Be in the precursor of 0 ~ 0.5 Silicalite-1 molecular sieve, go into still crystallization, washing, drying after stirring, last roasting promptly gets core-shell type molecular sieve Silicalite-1/HZSM-5.
Or,
S1 ' nuclear phase molecular sieve HZSM-5's is synthetic: adopt template through the synthetic SiO of the synthetic method of hydro-thermal
2/ Al
2O
3It is 25 ~ 300 HZSM-5 molecular sieve;
The preliminary treatment of S2 ' nuclear phase molecular sieve HZSM-5: adopt certain density acid or alkali at a certain temperature synthetic HZSM-5 molecular sieve to be carried out immersion treatment;
S3 ' core-shell molecular sieve Silicalite-1/HZSM-5's is synthetic: with above-mentioned be nuclear through the HZSM-5 of acid/alkali treatment molecular sieve, join TPAOH/SiO
2Be in 0 ~ 0.5 the Silicalite-1 molecular sieve precursor, to go into still crystallization, washing, drying after stirring, last roasting promptly gets core-shell type molecular sieve Silicalite-1/HZSM-5.
In the synthetic method of above-mentioned core-shell molecular sieve Silicalite-1/HZSM-5 catalyst, described template is at least a in TPAOH (TPAOH), tetraethyl ammonium hydroxide (TEAOH), the n-butylamine organic ammoniums such as (BTA).
In the synthetic method of above-mentioned core-shell molecular sieve Silicalite-1/HZSM-5 catalyst, described acid is to be selected from least a in the acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, citric acid; Described alkali is to be selected from least a in the organic bases such as KOH, NaOH, ammoniacal liquor or TPAOH, tetraethyl ammonium hydroxide, n-butylamine.
In the synthetic method of above-mentioned core-shell molecular sieve Silicalite-1/HZSM-5 catalyst, described pretreatment temperature is 20-100 ℃.
In the synthetic method of above-mentioned core-shell molecular sieve Silicalite-1/HZSM-5 catalyst, the time that described use acid or alkali are handled the HZSM-5 molecular sieve is 1 ~ 24 h.
In the synthetic method of above-mentioned core-shell molecular sieve Silicalite-1/HZSM-5 catalyst, the silicon source in the described Silicalite-1 molecular sieve precursor is to be selected from least a in ethyl orthosilicate TEOS, Ludox or the white carbon.
The present invention also provides a kind of preparation method of paraxylene, is raw material with toluene, Celfume, and under the described core-shell molecular sieve Silicalite-1/HZSM-5 of claim 1 catalyst action, methylation reaction makes.
Core-shell molecular sieve Silicalite-1/HZSM-5 catalyst provided by the present invention shows excellent more catalytic performance in the toluene methylation reaction, taken into account the conversion ratio and the paraxylene selectivity of toluene; Be the effective catalyst that a kind of selectivity prepares paraxylene, compare with other catalyst and have a clear superiority in.
[Brief Description Of Drawings]
Shown in Figure 1 is the sem photograph of nuclear phase molecular sieve HZSM-5;
Shown in Figure 2 is the sem photograph of the embodiment of the invention 1 prepared Silicalite-1/HZSM-5 core-shell molecular sieve catalyst;
Shown in Figure 3 is the sem photograph of the embodiment of the invention 4 prepared Silicalite-1/HZSM-5 core-shell molecular sieve catalyst;
Shown in Figure 4 is the sem photograph of the embodiment of the invention 5 prepared Silicalite-1/HZSM-5 core-shell molecular sieve catalyst;
Shown in Figure 5 is the sem photograph of the embodiment of the invention 10 prepared Silicalite-1/HZSM-5 core-shell molecular sieve catalyst;
Shown in Figure 6 is the sem photograph of the embodiment of the invention 11 prepared Silicalite-1/HZSM-5 core-shell molecular sieve catalyst;
Shown in Figure 7 is the XRD comparison diagram of nuclear phase molecular sieve HZSM-5 and the embodiment of the invention 1,11 prepared Silicalite-1/HZSM-5 core-shell molecular sieve catalyst.
[specific embodiment]
Below in conjunction with embodiments of the invention and comparative example the present invention is further specified:
One, Preparation of Catalyst
Embodiment 1
With TPAOH (TPAOH) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=50.It is silicon source, TPAOH/SiO that above-mentioned synthetic HZSM-5 molecular sieve is joined with TEOS
2In=0 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst A.
Embodiment 2
With triethylamine (TEA) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=150.It is silicon source, TPAOH/SiO that above-mentioned synthetic HZSM-5 molecular sieve is joined with the Ludox
2In=0.2 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst B.
Embodiment 3
With n-butylamine (BTA) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=250.It is silicon source, TPAOH/SiO that above-mentioned synthetic HZSM-5 molecular sieve is joined with the white carbon
2In=0.4 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst C.
Embodiment 4
With n-butylamine (BTA) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=100.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the citric acid solution of 0. 10M, handle 16 h down at 50 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with the Ludox
2In=0.12 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst D.
Embodiment 5
With 4-propyl bromide (TPABr) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=125.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the salpeter solution of 0.05M, handle 20 h down at 80 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with TEOS
2In=0.16 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst E.
Embodiment 6
With TPAOH (TPAOH) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=200.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the ammonia spirit of 0.25M, handle 24 h down at 70 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with the white carbon
2In=0.25 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst F.
Embodiment 7
With tetraethyl ammonium hydroxide (TEAOH) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=75.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the TPAOH solution of 0.30M, handle 12 h down at 90 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with TEOS
2In=0.30 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst G.
Embodiment 8
With the ethylenediamine is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=225.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the TEAOH solution of 0.15M, handle 22 h down at 60 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with the Ludox
2In=0.16 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst H.
Embodiment 9
With the triethanolamine is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=275.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the sulfuric acid solution of 2.5M, handle 2 h down at 100 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with the Ludox
2In=0.50 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst I.
Embodiment 10
With tetraethyl ammonium hydroxide (TEAOH) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=125.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the hydrobromic acid solution of 1.0M, handle 1 h down at 30 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with the white carbon
2In=0.40 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst J.
Embodiment 11
With TPAOH (TPAOH) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=240.Above-mentioned synthetic HZSM-5 molecular sieve is joined in the BTA solution of 1.5M, handle 18 h down at 60 ℃, it is silicon source, TPAOH/SiO that the HZSM-5 molecular sieve that will handle then joins with TEOS
2In=0.20 the Silicalite-1 molecular sieve precursor, stir, crystallization, washing, drying, roasting obtain catalyst K.
Comparative example 1
With TPAOH (TPAOH) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=150, be designated as catalyst L.
Comparative example 2
With n-butylamine (BTA) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=100, through the P of method load 5 wt% of dipping
2O
5, be designated as catalyst M.
Comparative example 3
With tetraethyl ammonium hydroxide (TEAOH) is template, through the synthetic method synthetic kernel phase molecule sieve HZSM-5 of hydro-thermal, wherein, SiO
2/ Al
2O
3=250, through the SiO of CLD method load 5 wt%
2, be designated as catalyst n.
Two, the preparation of paraxylene
Catalyst A ~ the N that makes in embodiment 1 ~ 11 and the comparative example is carried out performance evaluation on fixed bed reactors, wherein methylating reagent is a Celfume, and substrate is a toluene, and reaction condition and result see the following form 1.
Table 1 catalyst performance evaluation result
Toluene conversion %=[n (toluene sample size)-n (toluene surplus)]/n (toluene sample size) * 100
Paraxylene selectivity %=n (amount of paraxylene)/n (amount of xylenes) * 100
Experimental result from above-mentioned table can be found out; The core-shell molecular sieve Silicalite-1/HZSM-5 that the method that provides according to us is synthetic; In the toluene methylation reaction, show excellent more catalytic performance, taken into account the conversion ratio and the paraxylene selectivity of toluene.Be the effective catalyst that a kind of selectivity prepares paraxylene, compare with other catalyst and have a clear superiority in.
Accompanying drawing 1-6 is the sem photograph (SEM) of the above-mentioned synthetic Silicalite-1/HZSM-5 core-shell molecular sieve of nuclear phase molecular sieve HZSM-5 and part.As can be seen from the figure, synthetic its nuclear phase of core-shell molecular sieve (HZSM-5) is all wrapped up by shell facies, has covered the acidic site of nuclear phase molecular sieve HZSM-5 outer surface, thereby has improved the selectivity of paraxylene.
The core-shell molecular sieve A that accompanying drawing 7 makes for nuclear phase molecular sieve HZSM-5 and the foregoing description, the XRD comparison diagram of K; XRD curve through contrasting several kinds of molecular sieves can know that the core-shell molecular sieve Preparation of catalysts method that we provide can successfully synthesize the Silicalite-1/HZSM-5 core-shell molecular sieve.
Claims (9)
1. a core-shell molecular sieve Silicalite-1/HZSM-5 catalyst is characterized in that, adopts the method for growth in situ or diauxic growth to synthesize;
2. the synthetic method of a core-shell molecular sieve Silicalite-1/HZSM-5 catalyst comprises following step:
Nuclear phase molecular sieve HZSM-5's is synthetic: adopt template through the synthetic SiO of the synthetic method of hydro-thermal
2/ Al
2O
3It is 25 ~ 300 HZSM-5 molecular sieve;
Core-shell molecular sieve Silicalite-1/HZSM-5's is synthetic: with the HZSM-5 molecular sieve is nuclear, joins TPAOH/SiO
2Be in 0 ~ 0.5 the Silicalite-1 molecular sieve precursor, to go into still crystallization, washing, drying after stirring, last roasting promptly gets core-shell type molecular sieve Silicalite-1/HZSM-5.
3. the synthetic method of core-shell molecular sieve Silicalite-1/HZSM-5 catalyst according to claim 1; It is characterized in that, also comprise the pre-treatment step to the nuclear phase molecular sieve HZSM-5 after synthetic: employing concentration is that acid or the alkali of 0.05 ~ 2.5 mol/L carries out hydrothermal pretreatment to synthetic HZSM-5 molecular sieve.
4. the synthetic method of core-shell molecular sieve Silicalite-1/HZSM-5 catalyst according to claim 1 and 2; It is characterized in that described template is at least a in TPAOH (TPAOH), tetraethyl ammonium hydroxide (TEAOH), the n-butylamine organic ammoniums such as (BTA).
5. the synthetic method of core-shell molecular sieve Silicalite-1/HZSM-5 catalyst according to claim 1 and 2; It is characterized in that; Described acid is at least a in the acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, citric acid, and described alkali is at least a in the organic bases such as KOH, NaOH, ammoniacal liquor or TPAOH, tetraethyl ammonium hydroxide, n-butylamine.
6. the synthetic method of core-shell molecular sieve Silicalite-1/HZSM-5 catalyst according to claim 1 and 2 is characterized in that, described pretreatment temperature is 20-100 ℃.
7. the synthetic method of core-shell molecular sieve Silicalite-1/HZSM-5 catalyst according to claim 1 and 2 is characterized in that, the time that described use acid or alkali are handled the HZSM-5 molecular sieve is 1 ~ 24 h.
8. the synthetic method of core-shell molecular sieve Silicalite-1/HZSM-5 catalyst according to claim 1 and 2; It is characterized in that the silicon source in the described Silicalite-1 molecular sieve precursor is to be selected from least a in ethyl orthosilicate TEOS, Ludox or the white carbon.
9. the preparation method of a paraxylene is characterized in that, is raw material with toluene and Celfume, under the described core-shell molecular sieve Silicalite-1/HZSM-5 of claim 1 catalyst action, through methylation reaction, makes.
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Cited By (5)
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| CN103708496A (en) * | 2014-01-10 | 2014-04-09 | 湖南大学 | HZSM-5@silicalite-1 core-shell structure molecular sieve, and preparation method and application thereof |
| CN104557427A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon from oxygenated chemicals |
| CN106582785A (en) * | 2015-10-14 | 2017-04-26 | 神华集团有限责任公司 | Modified extruded catalyst used for alkylation reaction, and preparation method and application thereof |
| CN107930677A (en) * | 2016-10-12 | 2018-04-20 | 神华集团有限责任公司 | The preparation method of 5 catalyst of modified ZSM-5 for alkylated reaction and its preparation method and application and paraxylene |
| CN111569935A (en) * | 2020-05-22 | 2020-08-25 | 中国海洋石油集团有限公司 | Catalyst for preparing p-xylene, preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104557427A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon from oxygenated chemicals |
| CN104557427B (en) * | 2013-10-28 | 2016-08-17 | 中国石油化工股份有限公司 | The method of oxygenatedchemicals aromatic hydrocarbons |
| CN103708496A (en) * | 2014-01-10 | 2014-04-09 | 湖南大学 | HZSM-5@silicalite-1 core-shell structure molecular sieve, and preparation method and application thereof |
| CN103708496B (en) * | 2014-01-10 | 2015-08-19 | 湖南大学 | A kind of HZSM-5@silicalite-1 nucleocapsid structure molecular sieve and preparation method thereof and application |
| CN106582785A (en) * | 2015-10-14 | 2017-04-26 | 神华集团有限责任公司 | Modified extruded catalyst used for alkylation reaction, and preparation method and application thereof |
| CN107930677A (en) * | 2016-10-12 | 2018-04-20 | 神华集团有限责任公司 | The preparation method of 5 catalyst of modified ZSM-5 for alkylated reaction and its preparation method and application and paraxylene |
| CN107930677B (en) * | 2016-10-12 | 2020-10-27 | 神华集团有限责任公司 | Modified ZSM-5 catalyst for alkylation reaction, preparation method and application thereof, and preparation method of p-xylene |
| CN111569935A (en) * | 2020-05-22 | 2020-08-25 | 中国海洋石油集团有限公司 | Catalyst for preparing p-xylene, preparation method and application thereof |
| CN111569935B (en) * | 2020-05-22 | 2023-12-12 | 中国海洋石油集团有限公司 | Catalyst for preparing paraxylene and preparation method and application thereof |
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Application publication date: 20120919 |