CN102371176A - Catalyst for preparing aromatic hydrocarbon through methanol conversion and preparation method thereof - Google Patents
Catalyst for preparing aromatic hydrocarbon through methanol conversion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing aromatic hydrocarbon through methanol conversion and a preparation method thereof, and mainly solves the problems of complex technological process and low selectivity of the target product in the prior art. According to the invention, the catalyst comprises the following components of: by weight, a) 20-80 parts of a molecular sieve carrier; b) 0.5-12 parts of lanthanum element or its oxide which is carried on a); c) 0.5-10 parts of phosphor element or its oxide; d) 20-80 parts of a binder, wherein the molecular sieve comprises a mixture of HZSM-5 and at least one component selected from HZSM-11 or Hbeta molecular sieves; and the weight ratio of HZSM-5 to the at least one component selected from HZSM-11 or Hbeta is 0.1-10: 1. The technical scheme provided by the invention greatly solves the problems and can be used in the industrial production of aromatic hydrocarbon through methanol conversion.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of methanol conversion for preparing arene.
Background technology
Since China's oil and natural gas resource shortage, and coal resources are abundant relatively.In recent years, burning hot situation appears in China Coal Chemical Industry cause, the various places various Coal Chemical Industry projects that start one after another.As comparatively ripe coal chemical technology, coal-based synthesizing methanol becomes the first-selected project of most coal chemical industry enterprises.In recent years; China is that raw material production methyl alcohol is towards maximization, energy-saving development with coal; Output constantly increases, and therefore the production capacity of methyl alcohol will actively carry out the exploitation of Downstream Products of Methanol considerably beyond actual demand; Increase new methyl alcohol application, improve the production technology level of existing Downstream Products of Methanol, the development of methanol industry is had crucial meaning.
The methanol conversion research contents is very abundant.External Uop Inc., Lurgi company have developed MTO (methanol conversion system alkene respectively; Comprise ethene and propylene) and MTP (preparing propylene by methanol transformation) technology, Exxon-Mobil company has developed MTG (methanol conversion system gasoline) technology and MOGD (methanol conversion system petrol and diesel oil) 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 no matter see from present circumstances, be to be high-quality gasoline with methanol conversion, still is converted into alkene, and the economy of process is all hindered owing to the restriction that receives added value of product makes its industrialization process.
Aromatic hydrocarbons (especially benzene (Benzene), toluene (Toluene) and xylenes (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, and therefore, it is most important to seek a kind of new technology that can replace petrochemical industry to produce aromatic hydrocarbons.From the direct preparing aromatic hydrocarbon by converting of resourceful methyl alcohol,, has significant values 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.
CN 1880288A has introduced a kind of technology and catalyst of methanol conversion for preparing arene; This catalyst is carrier with the ZSM-5 molecular sieve with small crystal grains; 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
-1Catalyzed conversion is for aromatic hydrocarbons being main product under the condition, and 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-aromatic hydrocarbons through extract and separate.This technological essence is the methanol conversion technique for preparing gasoline, promptly on the basis of original methanol conversion technique for preparing gasoline, through the performance modulation of catalyst, makes 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 get into second stage reactor continue to react the second-stage reaction product, the process route flow process is comparatively complicated.
Summary of the invention
One of technical problem to be solved by this invention is complicated and target product aromatic hydrocarbons (especially BTX) problem that selectivity is not high 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 methanol conversion for preparing arene and has the high and high advantage of BTX selectivity of product of catalyst activity.Two of technical problem to be solved by this invention provides one of a kind of and technical solution problem corresponding methanol conversion for preparing arene Preparation of catalysts method.
For one of solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of catalyst of methanol conversion for preparing arene comprises in parts by weight: a) 20～80 parts of molecular sieve carriers; With the b that carries on it) 0.5～12 part of lanthanum element or its oxide; C) 0.5～10 part of P elements or its oxide; D) 20～80 parts of binding agents, wherein molecular sieve comprises HZSM-5 and is selected from least a mixture in HZSM-11 or the H beta-molecular sieve, HZSM-5 be selected from HZSM-11 or at least a weight ratio of H β is 0.1～10: 1.
In the technique scheme, the binding agent preferred version is Al
2O
3HZSM-5 be selected from HZSM-11 or at least a weight ratio preferable range of H β is 0.2～5: 1; In parts by weight, contain lanthanum element or its oxide preferable range in the catalyst being 1～8 part is 1～5 part with P elements or its oxide preferable range.
For solve the problems of the technologies described above two, the technical scheme that the present invention adopts is following:
(1) with the HZSM-5 of aequum and at least a and binding agent that is selected from HZSM-11 or H beta-molecular sieve mix 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; Pinch through mixing, moulding, drying, 500～600 ℃ of roastings be after 2～8 hours; Process catalyst carrier, wherein expanding agent is selected from the sesbania powder; (2),, process said methanol conversion for preparing arene catalyst through dry and 450～600 ℃ of roastings 2～6 hours with the lanthanum nitrate of said catalyst carrier load aequum and the acid that is selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate or the salt of aequum; Wherein, phosphorous acid or salt preferably phosphoric acid ammonium dihydrogen.
Contain two kinds of cross one another pore canal system in the ZSM-5 framework of molecular sieve; (pore structure has tangible shape selectivity to mononuclear aromatics to its duct size for 0.56nm * 0.53nm, 0.55nm * 0.51nm) approaching with the kinetic diameter of aromatic hydrocarbon molecule; So be widely used in aromatization; But because the acidity of ZSM-5 is stronger, catalyst is prone to coking deactivation, and therefore single molecular sieve catalyst is difficult to take into account acid matter of methanol conversion for preparing arene reaction pair 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.The H beta-molecular sieve has three-dimensional twelve-ring intersection pore passage structure, is the open system of no basket structure, helps the diffusion of molecule.ZSM-5 be selected from least a of HZSM-11 or H beta-molecular sieve and mix the intermodulation that can realize catalyst acid character and pore passage structure, thereby more help bringing 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%, and the BTX selectivity of product can reach more than 35%, has obtained better technical effect, and technological process is merely one section reaction, and is fairly simple.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
The present embodiment preparation comprises: in total catalyst weight, and 2%P
2O
5, 3%La
2O
3, 30%HZSM-5,10%HZSM-11,25%H β, 30%Al
2O
3Catalyst A.
Take by weighing 30 gram HZSM-5 molecular sieves, 10 gram HZSM-11 molecular sieves, 25 gram H beta-molecular sieves, 30 gram Al
2O
3, 38 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 6 hours, process the catalyst carrier of 2～3 millimeters long through drying, 520 ℃ of roastings.
20 gram said catalyst carrier impregnated in 14 milliliters contain 0.63 gram La
2O
3Lanthanum nitrate aqueous solution in, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, process catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 14 milliliters contain 0.42 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, process 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 100%, and the BTX selectivity of product is 35.29%.
[embodiment 2]
The present embodiment preparation comprises: in total catalyst weight, and 2%P
2O
5, 3%La
2O
3, 30%HZSM-5,18%HZSM-11,17%H β, 30%Al
2O
3Catalyst B.
The preparation method is identical with embodiment 1, and different is to take by weighing HZSM-11 molecular sieve 18 grams, H beta-molecular sieve 17 grams.
Catalyst examination 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 2%P
2O
5, 3%La
2O
3, 30%HZSM-5,25%HZSM-11,10%H β, 30%A1
2O
3Catalyst C.
The preparation method is identical with embodiment 1, and different is to take by weighing HZSM-11 molecular sieve 25 grams, H beta-molecular sieve 10 grams.
Catalyst examination 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 8%P
2O
5, 12%La
2O
3, 20%HZSM-5,15%HZSM-11,15%H β, 30%Al
2O
3Catalyst D.
Take by weighing 20 gram HZSM-5 molecular sieves, 15 gram HZSM-11 molecular sieves, 15 gram H beta-molecular sieves, 30 gram Al
2O
3, 3.2 gram sesbania powder, it is mixed, add 35 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 12 milliliters contain 3.0 gram La
2O
3Lanthanum nitrate aqueous solution in, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, process catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 12 milliliters contain 2.0 gram P
2O
5Ammonium dihydrogen phosphate aqueous solution in, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, process catalyst D.
Catalyst examination 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 3%P
2O
5, 5%La
2O
3, 60%HZSM-5,12%HZSM-11,20%Al
2O
3Catalyst E.
Take by weighing 60 gram HZSM-5 molecular sieves, 12 gram HZSM-11 molecular sieves, 20 gram Al
2O
3, 3.6 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 14 milliliters contain 1.09 gram La
2O
3Lanthanum nitrate aqueous solution in, in leaving standstill 24 hours, dry, 520 ℃ of roastings under the room temperature after 4 hours, process catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 14 milliliters contain 0.65 gram P
2O
5Ammonium dihydrogen phosphate aqueous solution in, in leaving standstill 4 hours, 520 ℃ roastings of 24 hours, 120 ℃ dryings under the room temperature after 4 hours, process catalyst E.
Catalyst examination 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 5%P
2O
5, 8%La
2O
3, 17%HZSM-5,50%H β, 20%Al
2O
3Catalyst F.
Take by weighing 17 gram HZSM-5 molecular sieves, 50 gram H beta-molecular sieves, 20 gram Al
2O
3, 3.5 gram sesbania powder, it is mixed, add 40 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 15 milliliters contain 1.84 gram La
2O
3Lanthanum nitrate aqueous solution in, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, process catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 15 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, process catalyst F.
Catalyst examination 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 5%La
2O
3, 65%HZSM-5,30%Al
2O
3Catalyst G.
Take by weighing 65 gram HZSM-5 molecular sieves, 30 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 mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 6 hours, process the catalyst carrier of 2～3 millimeters long through drying, 520 ℃ of roastings.
20 gram said catalyst carrier impregnated in 14 milliliters contain 1.05 gram La
2O
3Lanthanum nitrate aqueous solution in, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, process catalyst G.
Catalyst examination 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 2%La
2O
3, 3%Ga
2O
3, 65%HZSM-5,30%Al
2O
3Catalyst H.
Take by weighing 65 gram HZSM-5 molecular sieves, 30 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 mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 14 milliliters contain 0.63 gram Ga
2O
3The gallium nitrate aqueous solution in, in leaving standstill 24 hours, dry, 600 ℃ of roastings under the room temperature after 2 hours, process catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 14 milliliters contain 0.42 gram La
2O
3Lanthanum nitrate aqueous solution in, in leaving standstill 24 hours, dry, 600 ℃ of roastings under the room temperature after 2 hours, process catalyst H.
Catalyst examination 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 0.5%P
2O
5, 1%La
2O
3, 6.5%HZSM-5,6%HZSM-11,6%H β, 80%Al
2O
3Catalyst I.
Take by weighing 6.5 gram HZSM-5 molecular sieves, 6 gram HZSM-11 molecular sieves, 6 gram H beta-molecular sieves, 80 gram Al
2O
3, 4.0 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 15 milliliters contain 0.20 gram La
2O
3Lanthanum nitrate aqueous solution in, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, process catalyst intermediate.
Above-mentioned catalyst intermediate impregnated in 15 milliliters contain 0.10 gram P
2O
5Ammonium dihydrogen phosphate aqueous solution in, in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours, process catalyst I.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
Table 1 catalyst weight is formed (%)
| Example | Catalyst | HZSM-5 | HZSM-11 | Hβ | Al 2O 3 | Ga 2O 3 | La 2O 3 | P 2O 5 |
| Embodiment 1 | A | 30 | 10 | 25 | 30 | - | 3 | 2 |
| Embodiment 2 | B | 30 | 18 | 17 | 30 | - | 3 | 2 |
| Embodiment 3 | C | 30 | 25 | 10 | 30 | - | 3 | 2 |
| Embodiment 4 | D | 20 | 15 | 15 | 30 | - | 12 | 8 |
| Embodiment 5 | E | 60 | 12 | - | 20 | - | 5 | 3 |
| Embodiment 6 | F | 17 | - | 50 | 20 | - | 8 | 5 |
| Comparative example 1 | G | 65 | - | - | 30 | - | 5 | - |
| Comparative example 2 | H | 65 | - | - | 30 | 3 | 2 | - |
| Comparative example 3 | I | 6.5 | 6 | 6 | 80 | - | 1 | 0.5 |
The methanol conversion for preparing arene reaction result (wt%) of table 2 catalyst
Claims (5)
1. the catalyst of a methanol conversion for preparing arene comprises following component in parts by weight:
A) 20～80 parts of molecular sieve carriers; With carry on it
B) 0.5～12 part of lanthanum element or its oxide;
C) 0.5～10 part of P elements or its oxide;
D) 20～80 parts of binding agents;
Wherein molecular sieve comprises HZSM-5 and is selected from least a mixture in HZSM-11 or the H beta-molecular sieve, HZSM-5 be selected from HZSM-11 or at least a weight ratio of H β is 0.1～10: 1.
2. according to the catalyst of the said methanol conversion for preparing arene of claim 1, it is characterized in that binding agent is selected from Al
2O
3HZSM-5 be selected from HZSM-11 or at least a weight ratio of H β is 0.2～5: 1.
3. according to the catalyst of the said methanol conversion for preparing arene of claim 1, it is characterized in that, contain 1～8 part of lanthanum element or its oxide in the catalyst in parts by weight.
4. according to the catalyst of the said methanol conversion for preparing arene of claim 1, it is characterized in that, contain 1～5 part of P elements or its oxide in the catalyst in parts by weight.
5. the described methanol conversion for preparing arene Preparation of catalysts of claim 1 method may further comprise the steps successively:
(1) with the HZSM-5 of aequum and at least a and binding agent that is selected from HZSM-11 or H beta-molecular sieve mix 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; Pinch through mixing, moulding, drying, 500～600 ℃ of roastings be after 2～8 hours, processes catalyst carrier; Wherein expanding agent is selected from the sesbania powder;
(2),, process said methanol conversion for preparing arene catalyst through dry and 450～600 ℃ of roastings 2～6 hours with the lanthanum nitrate of said catalyst carrier load aequum and the acid that is selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate or the salt of aequum.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007985A (en) * | 2012-12-20 | 2013-04-03 | 清华大学 | Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof |
| CN104437594A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Low-wear fluidized bed catalyst for preparing aromatics from methanol and preparation method of low-wear fluidized bed catalyst for preparing aromatics from methanol |
| CN105665001A (en) * | 2016-01-07 | 2016-06-15 | 中石化炼化工程（集团）股份有限公司 | Catalyst for preparing aromatic hydrocarbons from methanol 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 |
| CN101671226A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Process for preparing dimethylbenzene by aromatization of methanol |
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Patent Citations (2)
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007985A (en) * | 2012-12-20 | 2013-04-03 | 清华大学 | Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof |
| CN103007985B (en) * | 2012-12-20 | 2014-09-24 | 清华大学 | Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof |
| CN104437594A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Low-wear fluidized bed catalyst for preparing aromatics from methanol and preparation method of low-wear fluidized bed catalyst for preparing aromatics from methanol |
| CN104437594B (en) * | 2013-09-24 | 2017-03-15 | 中国石油化工股份有限公司 | Low abrasion methanol aromatic hydrocarbons fluid catalyst and preparation method thereof |
| CN105665001A (en) * | 2016-01-07 | 2016-06-15 | 中石化炼化工程（集团）股份有限公司 | Catalyst for preparing aromatic hydrocarbons from methanol and preparation method thereof |
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