CN102371177B - Catalyst for preparing aromatic hydrocarbons by methanol conversion and preparation method thereof - Google Patents
Catalyst for preparing aromatic hydrocarbons by methanol conversion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing aromatic hydrocarbons by methanol conversion and a preparation method thereof, and mainly solves problems of complex technical route flow and low object product selectivity of a prior art. The catalyst comprises a) 20-80 parts of molecular sieve carrier, b) 0.1-20 parts of gallium element or oxide thereof carried by the molecular sieve carrier, c) 0.1-12 parts of lanthanum or phosphor element or oxide thereof, d) 20-80 parts of binder; and the molecular sieve comprises HZSM-5 and HMCM-22 in a mass ratio of 0.1-10:1. The invention also provides a preparation method of the catalyst. The above technical scheme well solves the problems and can be applied to industrial production of aromatic hydrocarbons by methanol conversion.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for methanol conversion for preparing arene.
Background technology
Aromatic hydrocarbons (especially benzene (Benzene), toluene (Toluene) and dimethylbenzene (Xylene), general designation BTX) be important petrochemical industry basic raw material, the aromatic hydrocarbons of China is mainly derived from petroleum resources, and the present situation of China's oil shortage of resources has determined the scarcity of aromatic hydrocarbon resource, therefore, find a kind of new technology that can replace petrochemical industry to produce aromatic hydrocarbons most important.
Due to China's oil and natural gas resource shortage, and coal resources are relatively abundant, in recent years, coal be take as raw material methanol is towards maximization, energy-saving development in China, output constantly increases, and the production capacity of methyl alcohol will, considerably beyond actual demand, therefore actively be carried out the exploitation of Downstream Products of Methanol, increase new methyl alcohol application, improve the production technology level of existing Downstream Products of Methanol, the development of methanol industry is had to very important meaning.From the direct preparing aromatic hydrocarbon by converting of resourceful methyl alcohol, for alleviating the shortage of aromatic hydrocarbons, the added value that improves Downstream Products of Methanol, prolongation Coal Chemical Industry and gas chemical industry's industrial chain, there is important value.
CN 1880288A has introduced a kind of technique and catalyst of methanol conversion for preparing arene, this catalyst be take ZSM-5 molecular sieve with small crystal grains as carrier, load active component gallium and lanthanum are that 0.1～5.0MPa, 300～460 ℃ of operating temperatures, raw material liq air speed are 0.1～6.0h at operating pressure
-1under condition, be catalytically conveted to and take aromatic hydrocarbons as main product, process refrigerated separation is by gas-phase product lower carbon number hydrocarbons and liquid product C
5 +hydrocarbon is separated, liquid product C
5 +hydrocarbon, through extract and separate, obtains aromatic hydrocarbons and non-aromatics.The essence of this technology is methanol conversion technique for preparing gasoline,, on the basis of original methanol conversion technique for preparing gasoline, by the performance modulation of catalyst, the arene content in product is increased.But this specification requirement ZSM-5 molecular sieve used is little crystal grain, and the gas-phase product lower carbon number hydrocarbons of one section of reaction enters second stage reactor and continues to react obtaining second-stage reaction product, and process route flow process is comparatively complicated.
Summary of the invention
One of technical problem to be solved by this invention is process route flow process complexity and the selective not high problem of target product aromatic hydrocarbons (especially BTX) existing in prior art.This catalyst has advantages of that for methanol conversion for preparing arene reaction catalyst activity is high and BTX selectivity of product is high.Two of problem to be solved by this invention is to provide a kind of preparation method for methanol conversion for preparing arene catalyst corresponding with one of technical solution problem.
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 for methanol conversion for preparing arene, comprises in parts by weight: a) 20～80 parts of molecular sieve carriers; With the b carrying thereon) 0.1～20 part of gallium element or its oxide; C) 0.1～12 part is selected from lanthanum or P elements or its oxide; D) 20～80 parts of binding agents, wherein molecular sieve comprises HZSM-5 and HMCM-22, the weight ratio of HZSM-5 and HMCM-22 is 0.1～10: 1.
In technique scheme, binding agent preferred version is Al
2o
3; The weight ratio preferred version of HZSM-5 and HMCM-22 is 0.2～5: 1.In parts by weight, in catalyst, containing gallium element or its oxide preferable range, it is 0.5～10 part and to be selected from lanthanum or P elements or its oxide preferable range be 0.5～8 part.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows:
(1) HZSM-5 of aequum, HMCM-22 and binding agent are mixed to get to mixture I, in mixture I, add the expanding agent of gained catalyst weight 0.5～5% and the aqueous solution of nitric acid of aequum, through kneading, moulding, dry, 500～600 ℃ of roastings, after 2～8 hours, make catalyst carrier; Wherein expanding agent is selected from sesbania powder; (2) by the acid or the salt that are selected from lanthanum nitrate or phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate of the salt that is selected from gallium nitrate or gallium sulfate of described catalyst carrier load aequum and aequum, drying and 450～600 ℃ of roastings 2～6 hours, make described for methanol conversion for preparing arene catalyst.
In ZSM-5 molecular sieve skeleton, contain two kinds of cross one another pore canal system, its pore size (0.56nm * 0.53nm, 0.55nm * 0.51nm) approach with the kinetic diameter of aromatic hydrocarbon molecule, pore structure has obvious shape selectivity to mononuclear aromatics, so be widely used in aromatization, but because the acidity of ZSM-5 is stronger, the easy coking deactivation of catalyst, therefore single molecular sieve catalyst is difficult to take into account methanol conversion for preparing arene reaction to Acidity and the synergistic requirement of pore passage structure.MCM-22 has two kinds of independently pore passage structures, except the two-dimentional dextrorotation duct with ten-ring of a kind of ZSM-5 of being similar to, also there are two supercages that inner space is respectively 0.71nm * 0.71nm * 1.82nm and 0.71nm * 0.71nm * 0.91nm, the existence of supercage has improved the appearance carbon ability of catalyst, and aromatisation stability is improved.The intermodulation that can realize catalyst acid character and pore passage structure that mixes of ZSM-5 and MCM-22, thus be more conducive to bring into play both synergies.Adopt catalyst of the present invention, for methanol conversion for preparing arene reaction, in continuous fixed bed reactors, 390 ℃ of pressure 0.3MPa, temperature, weight space velocity 2h
-1under condition, its methanol conversion can reach 100%, BTX selectivity of product and can reach more than 35%, has obtained good technique effect, and technological process is only one section of reaction, fairly simple.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
The present embodiment preparation comprises: in total catalyst weight, and 3%La
2o
3, 5%Ga
2o
3, 55%HZSM-5,17%HMCM-22,20%Al
2o
3catalyst A.
Take 55 grams of HZSM-5 molecular sieves, 17 grams of HMCM-22 molecular sieves, 20 grams of Al
2o
3, 3.6 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 40 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 600 ℃ of roastings, after 4 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 14 milliliters containing 1.09 grams of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst intermediate, after 6 hours, is made in standing 24 hours, dry, 450 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 14 milliliters containing 0.65 gram of La
2o
3lanthanum nitrate aqueous solution in, under room temperature, catalyst A, after 6 hours, is made in standing 24 hours, dry, 450 ℃ of roastings.
Adopt this catalyst to react for methanol conversion for preparing arene, in continuous fixed bed reactors, 390 ℃ of pressure 0.3MPa, temperature, weight space velocity 2h
-1under condition, its methanol conversion is that 100%, BTX selectivity of product is 37.45%.
[embodiment 2]
The present embodiment preparation comprises: in total catalyst weight, and 2%P
2o
5, 3%Ga
2o
3, 40%HZSM-5,25%HMCM-22,30%Al
2o
3catalyst B.
Take 40 grams of HZSM-5 molecular sieves, 25 grams of HMCM-22 molecular sieves, 30 grams of Al
2o
3, 3.8 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 40 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 520 ℃ of roastings, after 4 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 14 milliliters containing 0.63 gram of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst intermediate, after 4 hours, is made in standing 24 hours, dry, 480 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 14 milliliters containing 0.42 gram of P
2o
5ammonium dihydrogen phosphate aqueous solution in, under room temperature, catalyst B, after 4 hours, is made in standing 24 hours, dry, 480 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[embodiment 3]
The present embodiment preparation comprises: in total catalyst weight, and 5%La
2o
3, 8%Ga
2o
3, 20%HZSM-5,40%HMCM-22,27%Al
2o
3catalyst C.
Take 20 grams of HZSM-5 molecular sieves, 40 grams of HMCM-22 molecular sieves, 27 grams of Al
2o
3, 3.5 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 40 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 550 ℃ of roastings, after 4 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 14 milliliters containing 1.84 grams of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst intermediate, after 4 hours, is made in standing 24 hours, dry, 500 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 14 milliliters containing 1.15 grams of La
2o
3lanthanum nitrate aqueous solution in, under room temperature, catalyst C, after 4 hours, is made in standing 24 hours, dry, 500 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[embodiment 4]
The present embodiment preparation comprises: in total catalyst weight, and 3%P
2o
5, 2%Ga
2o
3, 15%HZSM-5,60%HMCM-22,20%Al
2o
3catalyst D.
Take 15 grams of HZSM-5 molecular sieves, 60 grams of HMCM-22 molecular sieves, 20 grams of Al
2o
3, 3.8 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 40 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 500 ℃ of roastings, after 6 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 14 milliliters containing 0.42 gram of Ga
2o
3the gallium sulfate aqueous solution in, under room temperature, catalyst intermediate, after 4 hours, is made in standing 24 hours, dry, 520 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 14 milliliters containing 0.63 gram of P
2o
5ammonium dibasic phosphate aqueous solution in, under room temperature, catalyst D, after 4 hours, is made in standing 24 hours, dry, 520 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[embodiment 5]
The present embodiment preparation comprises: in total catalyst weight, and 0.5%La
2o
3, 0.5%Ga
2o
3, 10%HZSM-5,10%HMCM-22,79%Al
2o
3catalyst E.
Take 10 grams of HZSM-5 molecular sieves, 10 grams of HMCM-22 molecular sieves, 79 grams of Al
2o
3, 4.0 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 45 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 600 ℃ of roastings, after 6 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 16 milliliters containing 0.10 gram of Ga
2o
3the gallium sulfate aqueous solution in, under room temperature, catalyst intermediate, after 3 hours, is made in standing 24 hours, dry, 550 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 16 milliliters containing 0.10 gram of La
2o
3lanthanum nitrate aqueous solution in, under room temperature, catalyst E, after 3 hours, is made in standing 24 hours, dry, 550 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[embodiment 6]
The present embodiment preparation comprises: in total catalyst weight, and 8%P
2o
8, 10%Ga
2o
3, 10%HZSM-5,50%HMCM-22,22%Al
2o
3catalyst F.
Take 10 grams of HZSM-5 molecular sieves, 50 grams of HMCM-22 molecular sieves, 22 grams of Al
2o
3, 3.2 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 40 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 520 ℃ of roastings, after 5 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 15 milliliters containing 2.44 grams of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst intermediate, after 2 hours, is made in standing 24 hours, dry, 600 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 15 milliliters containing 1.95 grams of P
2o
5phosphate aqueous solution in, under room temperature, catalyst F, after 2 hours, is made in standing 24 hours, dry, 600 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 1]
The preparation of this comparative example comprises: in total catalyst weight, and 2%Ga
2o
3, 68%HZSM-5,30%Al
2o
3catalyst G.
Take 68 grams of HZSM-5 molecular sieves, 30 grams of Al
2o
3, 3.9 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 40 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 520 ℃ of roastings, after 5 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 15 milliliters containing 0.41 gram of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst G, after 4 hours, is made in standing 24 hours, dry, 480 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 2]
The preparation of this comparative example comprises: in total catalyst weight, and 1%La
2o
3, 2%Ga
2o
3, 67%HMCM-22,30%Al
2o
3catalyst H.
Take 67 grams of HMCM-22 molecular sieves, 30 grams of Al
2o
3, 3.9 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 45 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 600 ℃ of roastings, after 4 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 16 milliliters containing 0.41 gram of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst intermediate, after 4 hours, is made in standing 24 hours, dry, 520 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 16 milliliters containing 0.21 gram of La
2o
3lanthanum nitrate aqueous solution in, under room temperature, catalyst H, after 4 hours, is made in standing 24 hours, dry, 520 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 3]
The preparation of this comparative example comprises: in total catalyst weight, and 1%P
2o
5, 1%Ga
2o
3, 18%HZSM-5,20%HMCM-22,60%Al
2o
3catalyst I.
Take 18 grams of HZSM-5 molecular sieves, 20 grams of HMCM-22 molecular sieves, 60 grams of Al
2o
3, 3.9 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 46 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 550 ℃ of roastings, after 6 hours, are made the catalyst carrier of 2～3 millimeters long.
20 grams of said catalyst carrier be impregnated in to 16 milliliters containing 0.20 gram of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst intermediate, after 6 hours, is made in standing 24 hours, dry, 450 ℃ of roastings.
Above-mentioned catalyst intermediate be impregnated in to 16 milliliters containing 0.20 gram of P
2o
5ammonium phosphate solution in, under room temperature, catalyst I, after 6 hours, is made in standing 24 hours, dry, 450 ℃ of roastings.
Catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
Table 1 catalyst weight forms (%)
| Example | Catalyst | HZSM-5 | HMCM-22 | Al 2O 3 | Ga 2O 3 | La 2O 3 | P 2O 5 |
| Embodiment 1 | A | 55 | 17 | 20 | 5 | 3 | - |
| Embodiment 2 | B | 40 | 25 | 30 | 3 | - | 2 |
| Embodiment 3 | C | 20 | 40 | 27 | 8 | 5 | - |
| Embodiment 4 | D | 15 | 60 | 20 | 2 | - | 3 |
| Embodiment 5 | E | 10 | 10 | 79 | 0.5 | 0.5 | - |
| Embodiment 6 | F | 10 | 50 | 22 | 10 | - | 8 |
| Comparative example 1 | G | 68 | - | 30 | 2 | - | - |
| Comparative example 2 | H | - | 67 | 30 | 2 | 1 | - |
| Comparative example 3 | I | 18 | 20 | 60 | 1 | - | 1 |
The methanol conversion for preparing arene reaction result (wt%) of table 2 catalyst
Claims (1)
1. for a method for methanol conversion for preparing arene, take 55 grams of HZSM-5 molecular sieves, 17 grams of HMCM-22 molecular sieves, 20 grams of Al
2o
3, 3.6 grams of sesbania powder, mixed, add the aqueous solution of nitric acid that 40 gram mass concentration are 5%, fully after kneading, be extruded into the cylindrical of 1.5 millimeters of diameters, drying, 600 ℃ of roastings, after 4 hours, are made the catalyst carrier of 2～3 millimeters long; 20 grams of said catalyst carrier be impregnated in to 14 milliliters containing 1.09 grams of Ga
2o
3the gallium nitrate aqueous solution in, under room temperature, catalyst intermediate, after 6 hours, is made in standing 24 hours, dry, 450 ℃ of roastings; Above-mentioned catalyst intermediate be impregnated in to 14 milliliters containing 0.65 gram of La
2o
3lanthanum nitrate aqueous solution in, under room temperature, catalyst A, after 6 hours, is made in standing 24 hours, dry, 450 ℃ of roastings; Employing is in total catalyst weight, 3%La
2o
3, 5%Ga
2o
3, 55%HZSM-5,17%HMCM-22,20%Al
2o
3catalyst A, for methanol conversion for preparing arene reaction, in fixed bed reactors continuously, 390 ℃ of pressure 0.3MPa, temperature, weight space velocity 2h
-1under condition, its methanol conversion is that 100%, BTX selectivity of product is 37.45%.
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| CN103418426B (en) * | 2012-05-16 | 2016-09-07 | 中国石油化工股份有限公司 | Binder-free methanol-to-aromatichydrocarbon hydrocarbon catalyst and preparation method thereof |
| CN104549440A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Adhesive-free oxy-compound aromatization catalyst and preparation method thereof |
| CN104549444B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application |
| CN104549441A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Small-crystal-grain ZSM-5 methanol aromatization catalyst |
| CN105254462B (en) * | 2015-11-03 | 2018-06-29 | 中国石油大学(华东) | A kind of technique of methanol-to-olefins co-production gasoline and aromatic hydrocarbons |
| EP3615208A1 (en) * | 2017-04-24 | 2020-03-04 | Basf Se | A molding comprising a zeolitic material, phosphorous, one or more metals and a binder |
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| CN101088614A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aromatized eutectic superfine zeolite grain catalyst and its prepn process and application |
| CN101671226A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Process for preparing dimethylbenzene by aromatization of methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088614A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aromatized eutectic superfine zeolite grain catalyst and its prepn process and application |
| CN101671226A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Process for preparing dimethylbenzene by aromatization of methanol |
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