CN102371178B - Catalyst for preparing arene by methanol conversion and preparation method thereof - Google Patents
Catalyst for preparing arene by methanol conversion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing arene by methanol conversion and a preparation method thereof. The problems of complex process route flow and low selectivity of a target product in the prior art are mainly solved. The problems are well solved by adopting the technical scheme that: the catalyst comprises the following components in part by weight: a) 20 to 80 parts of molecular sieve carrier, b) 0.1 to 12 parts of zinc element or oxide thereof carried on the molecular sieve carrier, c) 0.1 to 10 parts of nickel or phosphorus element or oxide thereof and d) 20 to 80 parts of adhesive, wherein the molecular sieve comprises a mixture of HZSM-5 and at least one of HZSM-11 and HMCM-22 molecular sieves, and the weight ratio of the HZSM-5 to the at least one of the HZSM-11 and the HMCM-22 is (0.1-10): 1. The catalyst can be used in the field of industrially producing the arene by methanol conversion.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of preparing aromatic hydrocarbon through methanol transformation.
Background technology
Since China's oil and natural gas resource shortage, and coal resources are relatively abundant.In recent years, burning hot situation appears in China Coal Chemical Industry cause, the various places various Coal Chemical Engineering Projects that start one after another.As comparatively ripe coal chemical technology, coal-based synthesizing methanol becomes the optimumitem of most coal chemical industry enterprises.In recent years, China is take coal as the raw material methanol towards maximization, energy-saving development, output constantly increases, the production capacity of methyl alcohol will be considerably beyond actual demand, therefore actively carry 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 very important meaning.
The methanol conversion research contents is very abundant.External Uop Inc., Lurgi company have developed respectively MTO (preparing olefin by conversion of methanol, comprise ethene and propylene) and MTP (preparing propylene by methanol transformation) technology, Exxon-Mobil company has developed MTG (methanol conversion gasoline processed) technology and MOGD (methanol conversion petrol and diesel oil processed) technology.Domestic such as the Dalian Chemistry and Physics Institute and Shanxi coalification etc. also methanol conversion has been carried out a large amount of research, and aspect two of catalyst and reaction process, obtained breakthrough.But from present circumstances, no matter be to be high-quality gasoline with methanol conversion, still be converted into alkene, the economy of process is all hindered owing to the restriction that is subjected to added value of product makes its industrialization process.
Aromatic hydrocarbons (especially benzene (Benzene), toluene (Toluene) and dimethylbenzene (Xylene) are referred to as BTX) is important petrochemical industry basic raw material, has high added value.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, seeks a kind of new technology that can replace petrochemical industry to produce aromatic hydrocarbons most important.From the direct preparing aromatic hydrocarbon by converting of resourceful methyl alcohol, for the shortage of alleviating aromatic hydrocarbons, the added value that improves Downstream Products of Methanol, prolongation Coal Chemical Industry and gas chemical industry's industrial chain, has important value.
CN 1880288A has introduced a kind of technique and catalyst of methanol conversion for preparing arene, this catalyst is 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
-1Be catalytically conveted under the condition take aromatic hydrocarbons as main product, the process refrigerated separation is with gas-phase product lower carbon number hydrocarbons and liquid product C
5 +Hydrocarbon separates, liquid product C
5 +Hydrocarbon obtains aromatic hydrocarbons and non-aromatics through extract and separate.The essence of this technology is the methanol conversion technique for preparing gasoline, namely on the basis of original methanol conversion technique for preparing gasoline, by the performance modulation of catalyst, so that the arene content in the product increases.But the used ZSM-5 molecular sieve of this specification requirement is little crystal grain, and the gas-phase product lower carbon number hydrocarbons of one section reaction enters second stage reactor and continue to react getting the second-stage reaction product, and the process route flow process is comparatively complicated.
Summary of the invention
One of technical problem to be solved by this invention is selectively not high problem of the complicated and target product aromatic hydrocarbons (especially BTX) of the process route flow process that exists in the prior art, and a kind of catalyst of new methanol conversion for preparing arene is provided.This catalyst is used for preparing aromatic hydrocarbon through methanol transformation and has advantages of that catalyst activity is high and the BTX selectivity of product is high.Two of technical problem to be solved by this invention provides a kind of preparation method of the preparing aromatic hydrocarbon through methanol transformation 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 of preparing aromatic hydrocarbon through methanol transformation comprises in parts by weight: a) 20～80 parts of molecular sieve carriers; With the b that carries thereon) 0.1～12 part of zinc element or its oxide; C) 0.1～10 part is selected from nickel or P elements or its oxide; D) 20～80 parts of binding agents, wherein molecular sieve comprises HZSM-5 and at least a mixture that is selected from HZSM-11 or the HMCM-22 molecular sieve, the HZSM-5 weight ratio at least a with being selected from HZSM-11 or HMCM-22 is 0.1～10: 1.
In the technique scheme, the binding agent preferred version is Al
2O
3The HZSM-5 weight ratio preferable range at least a with being selected from HZSM-11 or HMCM-22 is 0.2～5: 1; In parts by weight, contain zinc element or its oxide preferable range in the catalyst being 0.5～8 part is 0.5～5 part with being selected from nickel or P elements or its oxide preferable range.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows:
(1) HZSM-5 with aequum is mixed to get mixture I with at least a and binding agent that is selected from HZSM-11 or HMCM-22 molecular sieve, 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, drying, 500～600 ℃ of roastings after 2～8 hours, make catalyst carrier, wherein expanding agent is selected from the sesbania powder; (2) with the acid or the salt that are selected from nickel nitrate or phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate of the zinc nitrate of described catalyst carrier load aequum and aequum, described methanol conversion for preparing arene catalyst is made in drying and 450～600 ℃ of roastings 2～6 hours.
Contain two kinds of cross one another pore canal system in the ZSM-5 molecular sieve skeleton, its pore size (0.56nm * 0.53nm, 0.55nm * 0.51nm) kinetic diameter with aromatic hydrocarbon molecule approaches, 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 the methanol conversion for preparing arene reaction to Acidity and the synergistic requirement of pore passage structure.The ZSM-11 molecular sieve is applied in the aromatization owing to its unique pore passage structure and acid centre, and shows higher active and stable.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 have the inner space and be respectively two supercages of 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.ZSM-5 be selected from least a of ZSM-11 or MCM-22 molecular sieve and mix the intermodulation that can realize catalyst acid character and pore passage structure, thereby more be conducive to bring into play both synergies.Adopt catalyst of the present invention, be used for the methanol conversion for preparing arene reaction, in continuous fixed bed reactors, 390 ℃ of pressure 0.3MPa, temperature, weight space velocity 2h
-1Under the condition, its methanol conversion can reach 100%, BTX selectivity of product and can reach more than 35%, has obtained preferably technique effect, and technological process only is one section reaction, and is fairly simple.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
The present embodiment preparation comprises: in total catalyst weight, and 2%NiO, 3%ZnO, 45%HZSM-5,15%HZSM-11,15%HMCM-22,20%Al
2O
3Catalyst A.
Take by weighing 45 gram HZSM-5 molecular sieves, 15 gram HZSM-11 molecular sieves, 15 gram HMCM-22 molecular sieves, 20 gram Al
2O
3, 3.8 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 15 millimeters of diameters after the kneading, drying, 600 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 4 hours.
20 gram said catalyst carrier be impregnated in 14 milliliters of zinc nitrate aqueous solutions that contain 0.63 gram ZnO, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 14 milliliters of nickel nitrate aqueous solutions that contain 0.42 gram NiO, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, make catalyst A.
Adopt this catalyst to be used for the methanol conversion for preparing arene reaction, in continuous fixed bed reactors, 390 ℃ of pressure 0.3MPa, temperature, weight space velocity 2h
-1Under the condition, its methanol conversion is that 100%, BTX selectivity of product is 38.61%.
[embodiment 2]
The present embodiment preparation comprises: in total catalyst weight, and 5%P
2O
5, 8%ZnO, 30%HZSM-5,30%HZSM-11,7%HMCM-22,20%Al
2O
3Catalyst B.
Take by weighing 30 gram HZSM-5 molecular sieves, 30 gram HZSM-11 molecular sieves, 7 gram HMCM-22 molecular sieves, 20 gram Al
2O
3, 3.5 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 520 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 4 hours.
20 gram said catalyst carrier be impregnated in 14 milliliters of zinc nitrate aqueous solutions that contain 1.84 gram ZnO, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 14 milliliters contain 1.15 gram P
2O
5Ammonium dihydrogen phosphate aqueous solution in, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, make catalyst B.
The 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 3%NiO, 5%ZnO, 20%HZSM-5,12%HZSM-11,20%HMCM-22,40%Al
2O
3Catalyst C.
Take by weighing 20 gram HZSM-5 molecular sieves, 12 gram HZSM-11 molecular sieves, 20 gram HMCM-22 molecular sieves, 40 gram Al
2O
3, 3.7 gram sesbania powder, it is mixed, add 43 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 550 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 4 hours.
20 gram said catalyst carrier be impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 1.09 gram ZnO, in leaving standstill 24 hours, dry, 500 ℃ of roastings under the room temperature after 4 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 15 milliliters of nickel nitrate aqueous solutions that contain 0.65 gram NiO, in leaving standstill 24 hours, dry, 500 ℃ of roastings under the room temperature after 4 hours, make catalyst C.
The 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 1%NiO, 2%ZnO, 10%HZSM-5,7%HZSM-11,20%HMCM-22,60%Al
2O
3Catalyst D.
Take by weighing 10 gram HZSM-5 molecular sieves, 7 gram HZSM-11 molecular sieves, 20 gram HMCM-22 molecular sieves, 60 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 44 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 600 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 6 hours.
20 gram said catalyst carrier be impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 0.41 gram ZnO, in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 15 milliliters of nickel nitrate aqueous solutions that contain 0.21 gram NiO, in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours, make catalyst D.
The 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 1%P
2O
5, 0.5%ZnO, 5%HZSM-5,3.5%HZSM-11,10%HMCM-22,80%Al
2O
3Catalyst E.
Take by weighing 5 gram HZSM-5 molecular sieves, 3.5 gram HZSM-11 molecular sieves, 10 gram HMCM-22 molecular sieves, 80 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 600 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 6 hours.
20 gram said catalyst carrier be impregnated in 16 milliliters of zinc nitrate aqueous solutions that contain 0.10 gram ZnO, in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 16 milliliters contain 0.20 gram P
2O
5Phosphate aqueous solution in, in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours, make catalyst E.
The catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 1]
The preparation of this Comparative Examples comprises: in total catalyst weight, and 0.5%NiO, 1%ZnO, 68.5%HZSM-5,30%Al
2O
3Catalyst F.
Take by weighing 68.5 gram HZSM-5 molecular sieves, 30 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 520 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 5 hours.
20 gram said catalyst carrier be impregnated in 14 milliliters of zinc nitrate aqueous solutions that contain 0.20 gram ZnO, in leaving standstill 24 hours, dry, 600 ℃ of roastings under the room temperature after 2 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 14 milliliters of nickel nitrate aqueous solutions that contain 0.10 gram NiO, in leaving standstill 24 hours, dry, 600 ℃ of roastings under the room temperature after 2 hours, make catalyst F.
The catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 2]
The preparation of this Comparative Examples comprises: in total catalyst weight, and 1%P
2O
5, 2%ZnO, 30%HZSM-5,17%HZSM-11,50%Al
2O
3Catalyst G.
Take by weighing 30 gram HZSM-5 molecular sieves, 17 gram HZSM-11,50 gram A1
2O
3, 3.9 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 520 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 5 hours.
20 gram said catalyst carrier be impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 0.41 gram ZnO, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, make catalyst intermediate.
Above-mentioned catalyst intermediate be impregnated in 15 milliliters contain 0.21 gram P
2O
5Ammonium phosphate solution in, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, make catalyst G.
The catalyst test condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 3]
The preparation of this Comparative Examples comprises: in total catalyst weight, and 3%ZnO, 40%HZSM-5,10%HZSM-11,17%HMCM-22,30%Al
2O
3Catalyst H.
Take by weighing 40 gram HZSM-5 molecular sieves, 10 gram HZSM-11,17 gram HMCM-22 molecular sieves, 30 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 550 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 6 hours.
20 gram said catalyst carrier be impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 0.62 gram ZnO, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, make catalyst H.
The 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 | HZSM-11 | HMCM-22 | Al 2O 3 | ZnO | NiO | P 2O 5 |
| Embodiment 1 | A | 45 | 15 | 15 | 20 | 3 | 2 | - |
| Embodiment 2 | B | 30 | 30 | 7 | 20 | 8 | - | 5 |
| Embodiment 3 | C | 20 | 12 | 20 | 40 | 5 | 3 | - |
| Embodiment 4 | D | 10 | 7 | 20 | 60 | 2 | 1 | - |
| Embodiment 5 | E | 5 | 3.5 | 10 | 80 | 0.5 | - | 1 |
| Comparative example 1 | F | 68.5 | - | - | 30 | 1 | 0.5 | - |
| Comparative example 2 | G | 30 | 17 | - | 50 | 2 | - | 1 |
| Comparative example 3 | H | 40 | 10 | 17 | 30 | 3 | - | - |
The methanol conversion for preparing arene reaction result (wt%) of table 2 catalyst
Claims (1)
1. the catalyst of a preparing aromatic hydrocarbon through methanol transformation is in total catalyst weight, composed of the following components: 2%NiO, 3%ZnO, 45%HZSM-5,15%HZSM-11,15%HMCM-22,20%Al
2O
3
The preparation method of described catalyst is as follows: take by weighing 45 gram HZSM-5 molecular sieves, 15 gram HZSM-11 molecular sieves, 15 gram HMCM-22 molecular sieves, 20 gram Al
2O
3, 3.8 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully be extruded into the cylindrical of 1.5 millimeters of diameters after the kneading, drying, 600 ℃ of roastings were made the catalyst carrier of 2～3 millimeters long after 4 hours;
20 gram said catalyst carrier be impregnated in 14 milliliters of zinc nitrate aqueous solutions that contain 0.63 gram ZnO, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, make catalyst intermediate;
Above-mentioned catalyst intermediate be impregnated in 14 milliliters of nickel nitrate aqueous solutions that contain 0.42 gram NiO, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, make catalyst.
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| CN104549474A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst and preparation method thereof |
| RU2540333C1 (en) * | 2013-12-24 | 2015-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет тонких химических технологий имени М.В. Ломоносова" (МИТХТ им. М.В. Ломоносова) | Method of initiated continuous catalytic obtaining aromatic hydrocarbons from ethanol |
| RU2594564C1 (en) * | 2015-05-18 | 2016-08-20 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Catalyst and method of converting ethanol, methanol or mixture thereof |
| CN105949019B (en) * | 2016-04-29 | 2019-12-03 | 浙江大学 | A kind of catalyst and method improving methanol preparing aromatic hydrocarbon selectivity of product |
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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 |
| CN101172250A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| CN101596461A (en) * | 2008-06-02 | 2009-12-09 | 中国石油化工股份有限公司 | A kind of aromatizing catalyst for light hydrocarbon and preparation method thereof |
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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 |
| CN101172250A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Light hydrocarbon aromatization catalyst and its preparing process |
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