CN101934233B - Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas - Google Patents
Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas Download PDFInfo
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- CN101934233B CN101934233B CN2010102792365A CN201010279236A CN101934233B CN 101934233 B CN101934233 B CN 101934233B CN 2010102792365 A CN2010102792365 A CN 2010102792365A CN 201010279236 A CN201010279236 A CN 201010279236A CN 101934233 B CN101934233 B CN 101934233B
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Abstract
The invention relates to a preparation method of a catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas. The catalyst is prepared from Cu(NO)2.3H2O, Zn(NO)2.6H2O and HZSM-5(Si/Al=22) molecular sieves used as raw materials by a chemical homogeneous precipitation method. The utilized raw materials are nitrate and urea, and are inexpensive and easily obtained, no foreign ion is generated in reaction, trivial filter cake washing is not needed, and a pure catalyst with uniform particles and favorable dispersion can be obtained through high temperature baking. The invention has simple processes and novel method; and in a reaction that hydrogen is directly added into carbon monoxide to generate the dimethyl ether, the catalyst has very high activity and stability at the low temperature of 220-240 DEG C.
Description
Technical field
The present invention relates to the preparation method of a kind of Catalysts Cu-ZnO/HZSM-5 by direct synthesis of dimethyl ether from synthesis gas.
Background technology
Dimethyl ether (molecular formula: CH
3OCH
3Molecular weight: 46) be a kind of excellent solvent, can be used as pesticide, polishing agent, antirust agent, alkylating reagent, in addition also can be in aerosol, hair jelly, air freshener, domestic fuel etc., because the Cetane number height (55 ~ 60) of dimethyl ether, have good burning performance, tail gas pollution is little etc. when burning, so dimethyl ether has outstanding advantage as the alternative fuel of Diesel engine.Simultaneously, dimethyl ether still is a kind of good environmental friendliness cold-producing medium, compares with traditional fluorochlorohydrocarbon, and it is little less than destruction, greenhouse effects coefficient to ozone layer, and therefore, it is the clean energy resource of 21 century that dimethyl ether is described as.
At present, the preparation of dimethyl ether mainly contains two technologies, a strip adoption methanol dehydration technology, and methanol dehydration technology can be divided into liquid phase methanol dehydration and gas phase methanol dehydration again:
2CH
3OH?→?CH
3OCH
3?+?H
2O
Traditional liquid phase methanol dehydration adopts the concentrated sulfuric acid to make catalyst, has that reaction temperature is low, the conversion ratio advantages of higher, but seriously corroded, equipment is required high, and raffinate and waste water environmental pollution are serious, operating condition harshness, product post processing difficulty.This method is eliminated substantially at present.
General activated alumina or the alumina silicate etc. of adopting of gas-phase methanol dehydration are as catalyst, methanol steam is passed through solid catalyst, heterogeneous reaction takes place generate dimethyl ether, reaction temperature is 15 ~ 20MPa at 330 ~ 400 ℃, pressure generally, but the reaction temperature of this technology is harsher to the requirement of reaction unit than higher.
An other production technology of preparation dimethyl ether is to adopt synthesis gas (CO/H
2) directly synthetic.This technology is directly produced dimethyl ether by synthesis gas in a reactor under the bifunctional catalyst effect.Comparatively speaking, this method more and more receives the concern of industrial quarters owing to favourable and reasonable economically on thermodynamics, and the key reaction process of one-step technology is as follows:
4H
2?+?2CO?→?2CH
3OH
2CH
3OH?→?CH
3OCH
3?+?H
2O
CO?+?H
2O?→?CO
2?+?H
2
This shows, need a kind of bifunctional catalyst that has co hydrogenation and methanol dehydration simultaneously by synthesis of dimethyl ether with synthesis gas one-step, wherein, the catalyst of synthesizing methanol is mainly copper-based catalysts, and the catalyst of catalysis methanol dehydration mainly contains solid acids such as gama-alumina, HZSM-5, kaolin.
(Mx is one or both among V, Cr, Fe, Co, Ni, Zn, W or the Mo, and carrier is Al to adopt co-precipitation immersion process for preparing CuMnMx/ carrier among the Chinese invention patent ZL98107687.4
2O
3, ZrO
2, MgO, SiO
2Or one or both combinations in the molecular sieve) catalyst is at H
2/ CO=3/2(volume ratio), pressure is that 2.0MPa, reaction temperature are 250 ~ 270 ℃ and air speed 1500h
-1Condition under, the CO conversion ratio is 43 ~ 65%.Be that solvent, oxalates are that precipitating reagent prepares methanol synthesis catalyst with ethanol earlier among the Chinese invention patent ZL200410052571.6, make dimethyl ether synthetic catalyst with HZSM-5 type molecular sieve mechanical mixture again, to join the hydrogen biogas is raw material, is that 3.0 ~ 3.5MPa, reaction temperature are that 239 ~ 284 ℃, air speed are 2000 ~ 3000h at pressure
-1Condition under, the CO conversion ratio is 53.8 ~ 76.9%.Prepare dimethyl ether catalyst by methanol synthesis catalyst and the methanol dehydration catalyst mechanical mixture such as gama-alumina, HZSM-5 that consist of Cu-Zn-Al (O) among the Chinese invention patent ZL200710185215.5, at H
2/ CO=1(volume ratio), pressure is that 4.0MPa, reaction temperature are that 280 ℃ of following CO conversion ratios are 16.21 ~ 40.07%.Adopting Cu-Mn-Zn/ commodity molecular sieve in the Chinese invention patent application 200710139634.5 is dimethyl ether catalyst, at H
2/ CO=1.0(volume ratio), pressure is that 4.0MPa, reaction temperature are that 280 ℃ of following CO conversion ratios are 10.92 ~ 19.97%, the dimethyl ether selectivity is 60.1 ~ 80.9%.Chinese invention patent application 200810202609.1 is mixed with the catalyst that forms with acid modification kaolin and copper-based catalysts, at H
2/ CO=1(volume ratio), pressure is that 3.0MPa, reaction temperature are that 240 ~ 290 ℃ of following CO conversion ratios are 40 ~ 60%.Chinese invention patent application 200810046592.5 is a precipitating reagent with the alkali metal salt, adopts co-precipitation immersion process for preparing Cu-Zn-Al-Mg (O)-γ-Al
2O
3, at H
2/ CO=1.5 ~ 2.5(volume ratio), pressure is that 4.0 ~ 6.0MPa, reaction temperature are that 275 ~ 285 ℃ of following CO conversion ratios are about 80%, CO
2Selectivity is up to 28.53%.
This shows, generally adopt co-precipitation infusion process or mechanical mixing to prepare dimethyl ether synthetic catalyst at present, raw materials used is nitrate or acetate, and precipitating reagent mostly is alkali-metal hydroxide, carbonate or oxalates.Institute's controlling catalyst uniformity and dispersiveness are not high enough, and have the problems such as influence of foreign ion, and therefore, prepared catalyst activity is limited, to the requirement harshness of reaction condition.As: the pressure by direct synthesis of dimethyl ether from synthesis gas reaction in the above-mentioned patent mostly is greatly more than the 4.0MPa, and reaction temperature generally is higher than 250 ℃, and optimum working temperature is more than 280 ℃ even higher, and the conversion ratio of carbon monoxide yield low, dimethyl ether is low in the reaction.
Summary of the invention
The Preparation of catalysts method that the purpose of this invention is to provide the direct synthesis of dimethyl ether from synthesis gas of a kind of high activity, high selectivity and high stability.In this preparation method, raw material is cheap and easy to get, flow process is simple and clear, do not have any pollutant emission, is highly susceptible to the popularization of large-scale industrial production.
In order to overcome many deficiencies of traditional catalyst and preparation method, the present invention has made following improvement and innovation:
1, abandon traditional coprecipitation, adopt peculiar chemical Preparation by Uniform Precipitation catalyst, purpose is to simplify preparation flow, can obtain high dispersive, high activated catalyst simultaneously;
2, selecting nitrate (but not organic salt) is presoma, and purpose is in order to reduce cost of material and to reduce environmental pollution;
3, selecting urea is slow precipitating reagent, and purpose is that heat decomposition temperature is lower and can not produce impurity;
4, adopted the unlimited system (but not enclosed system of conventional high-tension reactor) that adds hot reflux continuously and the reaction solution of high dilution, purpose is in order to reduce the formation of metal ammonium complex ion, to reduce the waste and the loss of catalyst preparation process;
5, adopting acid stronger HZSM-5 (Si/Al=22) molecular sieve is carrier, promotes the chemical reaction process forward to carry out, and increases the selectivity of target product DME.
The present invention is to provide the preparation method of a kind of Catalysts Cu-ZnO/HZSM-5 of direct synthesis of dimethyl ether from synthesis gas, is with Cu (NO)
23H
2O, Zn (NO)
26H
2O, HZSM-5 (Si/Al=22) molecular sieve is a raw material, adopts chemical Preparation by Uniform Precipitation to form, and step is as follows:
(1) take by weighing a certain amount of Gerhardite and zinc nitrate hexahydrate, the mol ratio of control copper nitrate and zinc nitrate is 1:1 ~ 20:1, adds a certain amount of water, stirring and dissolving, and the mol ratio of control water and copper ion is 1700:1;
(2) take by weighing certain amount of urea and join in the above-mentioned mixed solution, stirring and dissolving, the mol ratio that control urea and copper nitrate add zinc nitrate is 2:1 ~ 4:1;
(3) add certain amount of H ZSM-5 (Si/Al=22) again, and vigorous stirring makes it to form the suspension of homogeneous, control HZSM-5 molecular sieve is 1:10 ~ 10:1 with the ratio that copper nitrate adds the quality of zinc nitrate;
(4) above-mentioned suspension is transferred in the three-neck flask, continued vigorous stirring 30 minutes;
(5) three-neck flask is positioned in the oil bath pan, is heated to 90 ~ 100 degrees centigrade, stir, refluxed 15 ~ 20 hours;
(6) treat that suspension PH reaches about 7.0, stop heating, suspension is cooled to room temperature immediately, after washing through decompress filter, with 200 ml deionized water, change 80 degrees centigrade of oven dryings 24 hours again over to;
(7) dried matter is put into Muffle furnace, be warming up to 350 degrees centigrade and roasting 4 hours with 2 degrees celsius/minute.Obtain highly active nucleocapsid shape Cu-ZnO(shell)/HZSM-5(nuclear) catalyst.
The Cu-ZnO/HZSM-5 catalyst of the present invention preparation is used for the reaction of the direct hydrogenation dimethyl ether synthesis of carbon monoxide, is 2.0MPa in reaction pressure, temperature between 220 ~ 280 ℃, reaction velocity 1500 h
-1And H
2/ CO=2(volume ratio) under the condition, the CO conversion ratio reaches as high as 90.9%.
The present invention is raw materials used to be nitrate and urea, cheap and easy to get, no any foreign ion generates in the reaction, need not to carry out loaded down with trivial details filter cake washing, can obtain uniform particles, finely disseminated pure catalyst through high-temperature roasting, operation of the present invention is simple, the method novelty, generate in the reaction of dimethyl ether at the direct hydrogenation of carbon monoxide, catalyst has very high activity and stable under 220 ~ 240 ℃ low temperature.
The specific embodiment
The present invention further describes with reference to the following example:
Embodiment 1
Take by weighing 9.418 gram Gerhardites and 5.801 gram zinc nitrate hexahydrates in beaker, add 1200 ml deionized water, stirring and dissolving takes by weighing 8.784 gram urea again and joins in the above-mentioned mixed liquor, treat urea dissolving after, add 4.690 gram HZSM-5 molecular sieves, and vigorous stirring makes it to form the suspension of homogeneous, and above-mentioned suspension is changed in the three-neck flask, continues to stir 30 minutes, three-neck flask is positioned in the oil bath pan, stirs and reflux heating 15 ~ 20 hours in 100 degrees centigrade.Treat that suspension PH reaches at 7.0 o'clock, stop heating, suspension is cooled to room temperature immediately, then decompress filter, wash with 200 ml deionized water, change 80 degrees centigrade of oven dryings 24 hours again over to, dried matter is put into Muffle furnace, be warming up to 350 degrees centigrade and roasting 4 hours with 2 degrees celsius/minute, obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 1:1.
Take by weighing with method for preparing, particle diameter is 20 ~ 40 purpose catalyst 2 grams, carries out the co hydrogenation activity rating in fixed bed reactors.Reaction condition: H
2/ CO=2(volume ratio), pressure 2 MPa, 220 ~ 280 ℃ of reaction temperatures, reactant air speed 1500h
-1The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 1:
Table 1 embodiment 1 activity of such catalysts evaluation result
Embodiment 2
With reference to preparation method and the step of embodiment 1, the amount of different is HZSM-5 is 3.126 grams.Obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 1.5:1.
By same method and condition the co hydrogenation activity of catalyst is estimated.The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 2:
Table 2 embodiment 2 activity of such catalysts evaluation results
Embodiment 3
With reference to preparation method and the step of embodiment 1, the amount of different is HZSM-5 is 2.680 grams.Obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 1.75:1.
By same method and condition the co hydrogenation activity of catalyst is estimated.The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 3:
Table 3 embodiment 3 activity of such catalysts evaluation results
Embodiment 4
With reference to preparation method and the step of embodiment 1, the amount of different is HZSM-5 is 2.345 grams.Obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 2:1.
By same method and condition the co hydrogenation activity of catalyst is estimated.The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 4:
Table 4 embodiment 4 activity of such catalysts evaluation results
Embodiment 5
With reference to preparation method and the step of embodiment 1, the amount of different is HZSM-5 is 1.876 grams.Obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 2.5:1.
By same method and condition the co hydrogenation activity of catalyst is estimated.The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 5:
Table 5 embodiment 5 activity of such catalysts evaluation results
Embodiment 6
With reference to preparation method and the step of embodiment 2, different is that oil bath temperature is adjusted into 95 degrees centigrade.Obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 1.5:1.
By same method and condition the co hydrogenation activity of catalyst is estimated.The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 6:
Table 6 embodiment 6 activity of such catalysts evaluation results
Embodiment 7
With reference to preparation method and the step of embodiment 3, different is that oil bath temperature is adjusted into 95 degrees centigrade.Obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 1.75:1.
By same method and condition the co hydrogenation activity of catalyst is estimated.The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 7:
Table 7 embodiment 7 activity of such catalysts evaluation results
Embodiment 8
With reference to preparation method and the step of embodiment 4, different is that oil bath temperature is adjusted into 95 degrees centigrade.Obtaining (cupric oxide+zinc oxide)/HZSM-5 weight ratio is the Cu-ZnO/HZSM-5 catalyst of 2:1.
By same method and condition the co hydrogenation activity of catalyst is estimated.The conversion ratio and the product selectivity of the reactant under the different temperatures are as shown in table 8:
Table 8 embodiment 8 activity of such catalysts evaluation results
Claims (2)
1. the preparation method of the Catalysts Cu O-ZnO/HZSM-5 of a direct synthesis of dimethyl ether from synthesis gas is characterized in that the (NO with Cu
3)
23H
2O, Zn (NO
3)
26H
2The HZSM-5 molecular sieve of O, Si/Al=22 is a raw material, adopts chemical Preparation by Uniform Precipitation to form, and step is as follows:
(1) take by weighing a certain amount of Gerhardite and zinc nitrate hexahydrate, the mol ratio of control copper nitrate and zinc nitrate is 1: 1～20: 1, adds a certain amount of water, stirring and dissolving, and the mol ratio of control water and copper ion is 1700: 1;
(2) take by weighing certain amount of urea and join in the above-mentioned mixed solution, stirring and dissolving, the mol ratio that control urea and copper nitrate add zinc nitrate is 2: 1～4: 1;
(3) add the HZSM-5 of a certain amount of Si/Al=22 again, and vigorous stirring makes it to form the suspension of homogeneous, control HZSM-5 molecular sieve is 1: 10～10: 1 with the ratio that copper nitrate adds the quality of zinc nitrate;
(4) above-mentioned suspension is transferred in the three-neck flask, continued vigorous stirring 30 minutes;
(5) three-neck flask is positioned in the oil bath pan, is heated to 90～100 degrees centigrade, stir, refluxed 15～20 hours;
(6) treat that suspension PH reaches 7.0, stop heating, suspension is cooled to room temperature immediately, after washing through decompress filter, with 200 ml deionized water, change 80 degrees centigrade of oven dryings 24 hours again over to;
(7) dried matter is put into Muffle furnace, be warming up to 350 degrees centigrade and roasting 4 hours, obtain highly active nucleocapsid shape CuO-ZnO/HZSM-5 catalyst with 2 degrees celsius/minute.
2. be used for the reaction of the direct hydrogenation dimethyl ether synthesis of carbon monoxide as the CuO-ZnO/HZSM-5 catalyst of claim 1 preparation, it is characterized in that reaction condition is: reaction temperature is 220～280 ℃, and reaction pressure is 2.0MPa, reaction velocity 1500h
-1And H
2/ CO=2 (volume ratio), the CO conversion ratio reaches as high as 90.9%.
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| CN102698762B (en) * | 2012-05-22 | 2013-12-11 | 太原理工大学 | Method for preparing dimethyl ether (DME) catalyst from synthesis gas |
| CN103910611A (en) * | 2013-01-09 | 2014-07-09 | 杨凯善 | Coal-based one-step synthesis method of dimethyl ether |
| CN103212418B (en) * | 2013-04-25 | 2015-05-20 | 太原理工大学 | Dual-function catalyst for directly preparing dimethyl ether from synthesis gas and preparation method of dual-function catalyst |
| GB201418475D0 (en) * | 2014-10-17 | 2014-12-03 | Johnson Matthey Plc | Catalyst and process |
| CN108745277B (en) * | 2018-06-07 | 2021-03-09 | 天津鼎芯膜科技有限公司 | Three-dimensional assembly core-shell structure material and preparation method and application thereof |
| CN110420658A (en) * | 2019-08-08 | 2019-11-08 | 中国科学院兰州化学物理研究所 | A kind of preparation and application of the bifunctional catalyst with core-shell structure |
| CN110560153B (en) * | 2019-09-24 | 2021-08-17 | 东北大学 | Aluminum-shared metal-zeolite bifunctional catalyst, and preparation method and application thereof |
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| CN1142021C (en) * | 2000-08-11 | 2004-03-17 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether |
| CN100553771C (en) * | 2005-06-22 | 2009-10-28 | 中国石油化工股份有限公司 | The catalyst that is used for direct preparation of dimethyl ether by using synthesis gas |
| CN101722029A (en) * | 2008-10-30 | 2010-06-09 | 邹运湖 | Method for preparing catalyst for synthesizing dimethyl ether on fluidized bed |
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