CN104437596A - Methanol to arene catalyst and preparation method thereof - Google Patents
Methanol to arene catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a methanol to arene catalyst and a preparation method thereof, mainly aiming at solving the technical problems that the acidity of an existing catalyst is covered and the catalysis activity is low in the preparation process. The methanol to arene catalyst comprises the following components in percentage by weight: 1) 10.0%-40.0% of a binder, 2) 20.0%-70.0% of a Zn-HZSM-5 molecular sieve, and 3) 0-60.0% of matrix, wherein the Zn-HZSM-5 molecular sieve is a ZSM-5 molecular sieve with a skeleton containing zinc obtained through ammonia exchange performed on a Zn contained molecular sieve synthesized through a one-step method. The problem is well solved, and the catalyst can be used for industrial production of arene from methanol.
Description
Technical field
The present invention relates to a kind of catalyst and method for preparing catalyst of Methanol aromatic hydrocarbons.
Background technology
Based on Organic Chemicals, the aromatic hydrocarbons of China more than 85% is all produced by petroleum path.On the one hand, China's oil and natural gas resource are very short, cause the production cost of aromatic hydrocarbons day by day to rise; On the other hand, coal resources in China relative abundance, the production capacity of a large amount of coal-based methanol finds new outlets.Based on above 2 points, actively develop coal-based methanol aromatic hydrocarbons and there is important strategic importance.
It is a typical acid catalyzed reaction that aromatization of methanol prepares aromatic hydrocarbons.Methyl alcohol is dehydration generation dimethyl ether under acidic site effect first, and dimethyl ether generates low-carbon alkene again under the effect of acidic site, and low-carbon alkene generates aromatic hydrocarbons further across complex processes such as oligomerisation, cyclisation, dehydrogenation, alkylation and de-alkyl.Acidity and the acid amount of catalyst have significant impact to reaction result.And common Methanol arenes catalytic agent is all take ZSM-5 molecular sieve as acid carrier, a certain amount of dehydrogenation metal component of load obtains, and wherein dehydrogenation metal is generally Ag, Zn, Ga, Cr, La etc.
The people such as Wang Jinying [chemistry of fuel journal.37 volume 5 phases in 2009,607-612] have studied aromatization of methanol performance on ZnZSM-5 prepared by infusion process, after finding ZSM-5 molecular sieve dipping Zn, the B acid position of molecular sieve is covered in a large number, and the quantity of strong acidic site also declines greatly simultaneously.
[chemical industry is in progress the people such as Liu Weiqiao.30 volume 12 phases in 2011,2637-2641] have studied Ga modification HZSM-5 molecular sieve on aromatization of methanol performance, result also finds, after infusion process load Ga, the B acid position of molecular sieve is covered in a large number, and the quantity of strong acidic site also declines greatly simultaneously.And strong acidic site is conducive to the methoxyl group species activating the formation of methanol adsorption, and this surperficial methoxyl group species can accelerate to activate middle hydro carbons and carry out aromatisation.
If adopt ion-exchange carried metal, then easily the H ion-exchange in ion-exchange sites is got off, the B number of acid sites of molecular sieve is declined greatly, also can suppress the selective of aromatization of methanol.Therefore select in synthesis ZSM-5 molecular sieve process, dehydrogenation metal to be incorporated in molecular sieve, metallic atom is made to occupy the skeleton of molecular sieve, dehydrogenation metal so just can be avoided to occupy the ion-exchange sites of molecular sieve, make molecular sieve can retain more B acid position and strong acidic site, improve the reactivity of catalyst.
Summary of the invention
One of technical problem to be solved by this invention is the existing Methanol arenes catalytic agent problem that acidity is capped in preparation process, catalytic activity is low, and provide the agent of a kind of Methanol arenes catalytic, it is many that this catalyst has strong acid center, the advantage that reactivity is high.
Two of technical problem to be solved by this invention is to provide the preparation method of a kind of skeleton corresponding with technical solution problem one containing the ZSM-5 molecular sieve of Zn.
Three of technical problem to be solved by this invention is to provide a kind of preparation method of the Methanol aromatic hydrocarbons fixed bde catalyst corresponding with technical solution problem one.
Four of technical problem to be solved by this invention is to provide a kind of preparation method of the Methanol aromatic hydrocarbons fluid catalyst corresponding with technical solution problem one.
Five of technical problem to be solved by this invention is to provide a kind of purposes of the catalyst corresponding with technical solution problem one.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of Methanol aromatic hydrocarbons, comprises following component by weight percentage:
1) binding agent of 10.0 ~ 40.0%;
2) the Zn-HZSM-5 molecular sieve of 20.0 ~ 70.0%;
3) matrix of 0 ~ 60.0%;
Wherein Zn-HZSM-5 molecular sieve is the ZSM-5 molecular sieve of framework of molecular sieve containing Zn of one-step synthesis method.
In technique scheme, binding agent is selected from least one in Alumina gel, acidifying Alumina gel, r-Al2O3 or boehmite.Zn-HZSM-5 molecular sieve is the molecular sieve of ZSM-5 molecular sieve after ammonium exchanges containing Zn of one-step synthesis method, and its silica alumina ratio SiO2/Al2O3 is 20 ~ 200.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: described skeleton, containing the preparation method of ZSM-5 molecular sieve of Zn, comprises following steps:
1) a certain amount of Ludox is mixed mutually with appropriate NaOH solution, stir and obtain Sol A;
2) join in Sol A by a certain amount of containing Zn solution, stir 0.1 ~ 2h; Wherein Zn solution is selected from least one in the ammonia spirit of zinc nitrate aqueous solution, zinc sulfate solution, zinc acetate solution, zinc citrate solution or zinc;
3) a certain amount of aluminium source is joined in said mixture, stir 0.1 ~ 2h; Wherein aluminium source is selected from least one in aluminum nitrate, aluminum sulfate aqueous solution;
4) mixture is proceeded in crystallization still, take out after 2 ~ 5 days in 150 ~ 180 DEG C of crystallization, after the washing and ammonium exchange of routine, obtain Zn-HZSM-5 molecular sieve through super-dry, roasting.
In technique scheme, preferred technical scheme, concrete building-up process comprises the following steps: 1) mixed mutually with appropriate NaOH solution by a certain amount of Ludox, stirs and obtains Sol A; 2) join in Sol A by a certain amount of containing Zn solution, stir 0.1 ~ 2h.Wherein Zn solution is selected from least one in the ammonia spirit of zinc nitrate aqueous solution, zinc sulfate solution, zinc acetate solution, zinc citrate solution or zinc; 3) a certain amount of aluminium source is joined in said mixture, stir 0.1 ~ 2h.Wherein aluminium source is selected from least one in aluminum nitrate, aluminum sulfate aqueous solution.4) mixture is proceeded in crystallization still, take out after 2 ~ 5 days in 150 ~ 180 DEG C of crystallization, after the washing and ammonium exchange of routine, obtain Zn-HZSM-5 molecular sieve through super-dry, roasting.
In technique scheme, described matrix is selected from kaolin or diatomite, when preparing the fluid catalyst of Methanol aromatic hydrocarbons, in order to the wear resistance increasing catalyst is used.Its content is 0 ~ 60% by weight percentage, preferably 20.0 ~ 50.0%.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the preparation method of described Methanol arenes catalytic agent, comprises following step:
1) take a certain amount of Zn-HZSM-5 molecular sieve, binding agent, extrusion aid and dispersant, mix;
2) in said mixture, add the dust technology of a certain amount of 1.0 ~ 5.0%, evenly mediate, and extrusion;
3) by the catalyst of extruded moulding through super-dry, burnt, obtain the fixed bde catalyst of Methanol aromatic hydrocarbons.
In technique scheme, preferred technical scheme, adopts following steps:
1) take a certain amount of Zn-HZSM-5 molecular sieve, binding agent, extrusion aid and dispersant, mix; In catalyst weight percent, molecular sieve content is 20.0 ~ 70.0%;
2) in said mixture, add the dust technology of a certain amount of 1.0 ~ 5.0%, mixture is kneaded into and is suitable for extruded moulding state, and extrusion;
3) by the catalyst of extruded moulding through super-dry, burnt, obtain the fixed bde catalyst of Methanol aromatic hydrocarbons.
For solve the problems of the technologies described above four, the technical solution used in the present invention is as follows: the preparation method of described Methanol arenes catalytic agent, comprises following step:
1) take a certain amount of Zn-HZSM-5 molecular sieve, binding agent, matrix, mix with appropriate water, strongly mix 10 ~ 200 minutes;
2) spray-dired method is adopted to be prepared into the microballoon of 20 ~ 200 μm in above-mentioned slurries;
3) microballoon spraying dry obtained through super-dry, burnt, obtain Methanol aromatic hydrocarbons fluid catalyst.
In technique scheme, preferred technical scheme, when prepare be fluid catalyst time, adopt following steps:
1) take a certain amount of Zn-HZSM-5 molecular sieve, binding agent, matrix, mix with appropriate water, adopt colloid mill strongly to mix 10 ~ 60 minutes;
2) spray-dired method is adopted to be prepared into the microballoon of 20 ~ 200 μm in above-mentioned slurries;
3) microballoon spraying dry obtained through super-dry, burnt, obtain Methanol aromatic hydrocarbons fluid catalyst.
For solve the problems of the technologies described above five, the technical solution used in the present invention is as follows: a kind of method of Methanol aromatic hydrocarbons, take methyl alcohol as raw material, is 300 ~ 600 DEG C in reaction temperature, reaction pressure 0.01 ~ 1MPa, and methanol weight air speed is 0.1 ~ 8h
-1, water/methanol weight ratio is under the condition of 0 ~ 5, and raw material is by beds and any one catalyst exposure above-mentioned, and reaction generates the product based on aromatic hydrocarbons.
In technique scheme, preferred technical scheme take methyl alcohol as raw material, is 350 ~ 550 DEG C in reaction temperature, reaction pressure 0.1 ~ 1MPa, and methanol weight air speed is 0.2 ~ 6h
-1, water/methanol weight ratio is under the condition of 0.5 ~ 4, and raw material is by beds, and reaction generates the product based on aromatic hydrocarbons.
Directly dehydrogenation metal Zn is incorporated in molecular sieve owing to present invention employs in the process of synthesis ZSM-5 molecular sieve, Zn atom is made to occupy in the skeleton of molecular sieve, avoid the process of follow-up infusion process or ion-exchange load dehydrogenation metal Zn on a catalyst, thus avoid the B acid position that Zn atom occupies molecular sieve in a large number, the B acid position of catalyst and strong acid center is caused to decline, the problem that reactivity declines.Catalyst provided by the invention has the advantage that strong acidic site is many, reactivity is high, reaction temperature 430 DEG C, and mass space velocity=2.0h
-1, under the reaction condition of normal pressure, aromatics yield reaches more than 55%, BTX(benzene, toluene and dimethylbenzene) yield more than 44%, the catalyst all prepared higher than adopting infusion process and ion-exchange load dehydrogenation metal, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.But the present invention is not limited in these embodiments.
Detailed description of the invention
[embodiment 1]
Get 900g Ludox (SiO2 concentration 40%), the mixing of 88gNaOH and 1500g water, stir and obtain Sol A.Get 59.6g zinc nitrate and to be dissolved in 80g ammoniacal liquor obtaining solution B.Slowly added in A by B, limit edged stirs, and continues subsequently to stir 2h, obtains mixture C.Getting 75.2g aluminum nitrate is dissolved in 600g water, adds subsequently in mixture C, continues to stir 2h.Mixture is transferred to stainless steel crystallization still, in 180 degree of crystallization 3 days, after taking-up through the washing of routine, that ammonium exchanges, dry, roasting obtains Zn-HZSM-5 molecular sieve is for subsequent use.The silica alumina ratio SiO2/Al2O3 of molecular sieve is 60, and in molecular sieve, the mass content of Zn is 1.8 %.
Get Zn-HZSM-5 molecular sieve prepared by 39.0g said method, 24g boehmite and a small amount of extrusion aid, add the dust technology that appropriate mass concentration is 2.0% after mixing, until be kneaded into the state of applicable extruded moulding, and extrusion.By the catalyst of extruded moulding through 120 DEG C of dry 8h, 550 DEG C of roasting 4h obtain Methanol arenes catalytic agent H.
[embodiment 2]
Get the Zn-HZSM-5 molecular sieve of preparation in 30.0g embodiment 1,35g boehmite and a small amount of extrusion aid, add the dust technology that appropriate mass concentration is 1.5% after mixing, until be kneaded into the state of applicable extruded moulding, and extrusion.By the catalyst of extruded moulding through 110 DEG C of dry 12h, 560 DEG C of roasting 4h obtain Methanol arenes catalytic agent I.
[embodiment 3]
Get the Zn-HZSM-5 molecular sieve of preparation in 24.0g embodiment 1,50g boehmite and a small amount of extrusion aid, add the dust technology that appropriate mass concentration is 4.0% after mixing, until be kneaded into the state of applicable extruded moulding, and extrusion.By the catalyst of extruded moulding through 100 DEG C of dry 16h, 580 DEG C of roasting 3h obtain Methanol arenes catalytic agent J.
[embodiment 4]
Get the mixing of the Zn-HZSM-5 molecular sieve of preparation in 100g embodiment 1,112g kaolin, 180g Alumina gel (Al2O3 mass concentration is 21%) and 180g water, colloid mill is adopted strongly to mix 30 minutes, then spray-dired mode is adopted to be prepared into the microballoon of 20 ~ 200 μm, finally by microballoon through 110 DEG C of dry 12h, 560 DEG C of roasting 4h obtain Methanol arenes catalytic agent K.
[embodiment 5]
Get the mixing of the Zn-HZSM-5 molecular sieve of preparation in 70g embodiment 1,50g diatomite, 100g acidifying Alumina gel (Al2O3 mass concentration is 18%) and 100g water, colloid mill is adopted strongly to mix 40 minutes, then spray-dired mode is adopted to be prepared into the microballoon of 20 ~ 200 μm, finally by microballoon through 120 DEG C of dry 10h, 580 DEG C of roasting 4h obtain Methanol arenes catalytic agent L.
[comparative example 1]
Getting 300g silica alumina ratio SiO2/Al2O3 is the ZSM-5 molecular sieve of 60, and conventional conventional ammonium exchanges, and through super-dry, that roasting is prepared into HZSM-5 molecular sieve is for subsequent use.
Get the above-mentioned HZSM-5 molecular sieve of 50.0g, join in 300g zinc nitrate aqueous solution (ZnO mass concentration is 3%), add thermal agitation 2h in 90 DEG C, filter.Repeat by filtration cakes torrefaction after twice above-mentioned steps, 550 DEG C of roasting 6h obtain the ZnHZSM-5 molecular sieve of ion-exchange type, and in molecular sieve, the mass content of Zn is 2.0%.
Get ion-exchange type ZnHZSM-5 molecular sieve prepared by 39.0g said method, 24g boehmite and a small amount of extrusion aid, add the dust technology that appropriate mass concentration is 2.0% after mixing, until be kneaded into the state of applicable extruded moulding, and extrusion.By the catalyst of extruded moulding through 120 DEG C of dry 8h, 550 DEG C of roasting 4h obtain Methanol arenes catalytic agent M.
[comparative example 2]
Get the HZSM-5 molecular sieve of preparation in 150.0g comparative example 1, join in 120g zinc nitrate aqueous solution, evaporated by excessive moisture through super-dry after mixing, 550 DEG C of roastings subsequently obtain the ZnHZSM-5 molecular sieve of immersion-type, and in molecular sieve, the mass content of Zn is 2.0%.
Get immersion-type ZnHZSM-5 molecular sieve prepared by 39.0g said method, 24g boehmite and a small amount of extrusion aid, add the dust technology that appropriate mass concentration is 2.0% after mixing, until be kneaded into the state of applicable extruded moulding, and extrusion.By the catalyst of extruded moulding through 120 DEG C of dry 8h, 550 DEG C of roasting 4h obtain Methanol arenes catalytic agent N.
[comparative example 3]
Get the mixing of the immersion-type ZnHZSM-5 molecular sieve of preparation in 100g comparative example 2,112g kaolin, 180g Alumina gel and 180g water, colloid mill is adopted strongly to mix 30 minutes, then spray-dired mode is adopted to be prepared into the microballoon of 20 ~ 200 μm, finally by microballoon through 110 DEG C of dry 12h, 560 DEG C of roasting 4h obtain Methanol arenes catalytic agent O.
Reaction temperature 430 DEG C, mass space velocity=2.0h
-1, normal pressure, the reaction time is under the reaction condition of 1h, and the aromatization of methanol reaction result of each catalyst is listed in table 1, and wherein BTX representative represents benzene, toluene and dimethylbenzene respectively.
Table 1
| Embodiment | Catalyst | Aromatics quality yield/% | BTX mass yield/% |
| Embodiment 1 | H | 55.7 | 44.2 |
| Embodiment 2 | I | 50.4 | 40.1 |
| Embodiment 3 | J | 48.3 | 38.9 |
| Embodiment 4 | K | 48.7 | 39.6 |
| Embodiment 5 | L | 51.4 | 43.0 |
| Comparative example 1 | M | 53.4 | 41.9 |
| Comparative example 2 | N | 55.5 | 43.8 |
| Comparative example 3 | O | 47.8 | 37.8 |
Claims (10)
1. a catalyst for Methanol aromatic hydrocarbons, in catalyst weight percent, comprises following component:
1) binding agent of 10.0 ~ 40.0%;
2) the Zn-HZSM-5 molecular sieve of 20.0 ~ 70.0%;
3) matrix of 0 ~ 60.0%;
Wherein Zn-HZSM-5 molecular sieve is the ZSM-5 molecular sieve of skeleton containing Zn of one-step synthesis method.
2. Methanol arenes catalytic according to claim 1 agent, is characterized in that binding agent is selected from least one in Alumina gel, acidifying Alumina gel, r-Al2O3 or boehmite.
3. Methanol arenes catalytic according to claim 1 agent, is characterized in that described Zn-HZSM-5 molecular sieve is the ZSM-5 molecular sieve of skeleton containing Zn of one-step synthesis method, then ZSM-5 molecular sieve obtained after ammonium exchanges, its SiO
2/ Al
2o
3mole silica alumina ratio is 20 ~ 200.
4. skeleton according to claim 1 is containing the preparation method of the ZSM-5 molecular sieve of Zn, comprises following steps:
1) a certain amount of silicon source is mixed mutually with appropriate aqueous slkali, stir and obtain Sol A;
2) join in Sol A by a certain amount of containing Zn solution, stir 0.1 ~ 2h; Wherein Zn solution is selected from least one in the ammonia spirit of zinc nitrate aqueous solution, zinc sulfate solution, zinc acetate solution, zinc citrate solution or zinc;
3) a certain amount of aluminium source is joined in said mixture, stir 0.1 ~ 2h; Wherein aluminium source is selected from least one in aluminum nitrate, aluminum sulfate aqueous solution;
4) mixture is proceeded in crystallization still, take out after 2 ~ 5 days in 150 ~ 180 DEG C of crystallization, after the washing and ammonium exchange of routine, obtain Zn-HZSM-5 molecular sieve through super-dry, roasting.
5. skeleton according to claim 4 is containing the preparation method of the ZSM-5 molecular sieve of Zn, it is characterized in that silicon source is Ludox or sodium metasilicate; Aqueous slkali is NaOH or potassium hydroxide solution; When prepared catalyst is fluid catalyst, catalyst mesostroma comprises kaolin or diatomite, and its content, in catalyst weight percent, is 10 ~ 60%.
6. the preparation method of Methanol arenes catalytic according to claim 1 agent, comprises following step:
1) take a certain amount of Zn-HZSM-5 molecular sieve, binding agent, extrusion aid and dispersant, mix;
2) in said mixture, add the dust technology of a certain amount of 1.0 ~ 5.0%, evenly mediate, and extrusion;
3) by the catalyst of extruded moulding through super-dry, burnt, obtain the fixed bde catalyst of Methanol aromatic hydrocarbons.
7. the preparation method of Methanol arenes catalytic according to claim 1 agent, comprises following step:
1) take a certain amount of Zn-HZSM-5 molecular sieve, binding agent, matrix, mix with appropriate water, strongly mix 10 ~ 200 minutes;
2) spray-dired method is adopted to be prepared into the microballoon of 20 ~ 200 μm in above-mentioned slurries;
3) microballoon spraying dry obtained through super-dry, burnt, obtain Methanol aromatic hydrocarbons fluid catalyst.
8. the preparation method of Methanol arenes catalytic according to claim 7 agent, is characterized in that adopting colloid mill strongly to mix 10 ~ 60 minutes in step 1).
9. a method for Methanol aromatic hydrocarbons, taking methyl alcohol as raw material, is 300 ~ 600 DEG C in reaction temperature, reaction pressure 0.01 ~ 1MPa, and methanol weight air speed is 0.1 ~ 8h
-1, water/methanol weight ratio is under the condition of 0 ~ 5, and raw material is by any one catalyst exposure in beds and claim 1 ~ 3, and reaction generates the product based on aromatic hydrocarbons.
10. the method for Methanol aromatic hydrocarbons according to claim 9, taking methyl alcohol as raw material, is 350 ~ 550 DEG C in reaction temperature, reaction pressure 0.1 ~ 1MPa, and methanol weight air speed is 0.2 ~ 6h
-1, water/methanol weight ratio is under the condition of 0.5 ~ 4, and raw material is by beds, and reaction generates the product based on aromatic hydrocarbons.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435839A (en) * | 2015-12-07 | 2016-03-30 | 中国海洋石油总公司 | Methanol to aromatic catalyst containing two molecular sieves and preparation method |
| CN106986735A (en) * | 2017-04-18 | 2017-07-28 | 沈益明 | A kind of method that methanol based on loose structure Zeolite molecular sieve catalysis prepares aromatic hydrocarbons |
| CN114433192A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon from methanol and preparation method and application thereof |
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| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
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2013
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| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435839A (en) * | 2015-12-07 | 2016-03-30 | 中国海洋石油总公司 | Methanol to aromatic catalyst containing two molecular sieves and preparation method |
| CN106986735A (en) * | 2017-04-18 | 2017-07-28 | 沈益明 | A kind of method that methanol based on loose structure Zeolite molecular sieve catalysis prepares aromatic hydrocarbons |
| CN106986735B (en) * | 2017-04-18 | 2019-11-15 | 罗帮亮 | A method of the methanol based on porous structure Zeolite molecular sieve catalysis prepares aromatic hydrocarbons |
| CN114433192A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon from methanol and preparation method and application thereof |
| CN114433192B (en) * | 2020-10-20 | 2024-02-02 | 中国石油化工股份有限公司 | Catalyst for preparing arene from methanol, and preparation method and application thereof |
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