CN102795598A - Method for reforming dimethyl ether water steam to generate hydrogen - Google Patents

Method for reforming dimethyl ether water steam to generate hydrogen Download PDF

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CN102795598A
CN102795598A CN201110139959XA CN201110139959A CN102795598A CN 102795598 A CN102795598 A CN 102795598A CN 201110139959X A CN201110139959X A CN 201110139959XA CN 201110139959 A CN201110139959 A CN 201110139959A CN 102795598 A CN102795598 A CN 102795598A
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dimethyl ether
mass ratio
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reaction
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CN102795598B (en
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陈光文
杨梅
李淑莲
焦凤军
门勇
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a method for reforming dimethyl ether water steam to generate hydrogen, which mainly solves the problems of the prior art that the conversion rate of dimethyl ether is low and the stability of a catalyst is poor. The technical scheme is as follows: the method taking the dimethyl ether (DME) and water as raw materials comprises the following steps of: mixing the water steam with the dimethyl ether in a fixed bed reactor in a ratio of 3-7 under the conditions that the reaction temperature is 380-470 DEG C and a reaction air speed is 1000-22000/h; and pre-heating and contacting the mixture with a ZnO-ZnM2O4/TiO2-Al2O3 (M is Cr, Al and the like) catalyst to generate reformed gas enriched with the hydrogen. In the ZnO-ZnM2O4/TiO2-Al2O3 catalyst, the mol ratio of ZnO to ZnM2O4 is more than or equal to 2; the mol ratio of ZnO to ZnAl2O4 is more than 0; the mass ratio of TiO2 to Al2O3 is 0.03-0.2; and the mass ratio of ZnO-ZnM2O4 to TiO2-Al2O3 is 0.33-5. According to the method disclosed by the invention, the catalytic conversion rate of the dimethyl is up to 100%, the CO selectivity is low, a methane reaction does not happen, the preparation cost of the catalyst is low, the reduction is not needed and the stability is good, so that the method can be used for industrial production.

Description

A kind of method of dimethyl ether-steam reforming hydrogen manufacturing
Technical field
The present invention relates to a kind of method of dimethyl ether-steam reforming hydrogen manufacturing, relate in particular to about adopting ZnO-ZnM xO y/ TiO 2-Al 2O 3(x>=1, y>=2, x, y ∈ N, M are Cr, Al etc.) for the method for catalyzer realization dimethyl ether-steam reforming hydrogen manufacturing, belong to chemical industry and energy field.
Background technology
Hydrogen is to have one of sustainable energy of development potentiality this century most as a kind of cleaning, efficient, the safe energy.It is a kind of secondhand energy, must utilize hydrogeneous raw material to produce through certain method.Wherein, with fossil oil or renewable energy source be vapor reforming hydrogen production process, by product CO content low receive much attention high of raw material because of hydrogen output.Dme is as a kind of new energy carrier, has high H/C ratio, no C-C key, energy density is big and advantage such as nontoxic.In addition, the physical properties of dme is similar to liquefied gas, is prone to store and transportation, can be compatible mutually with the Infrastructure of existing LPG liquefied petroleum gas.Therefore, be that to carry out vapor reforming hydrogen production be a kind of comparatively ideal hydrogen supply approach to raw material with the dme.
It is generally acknowledged that dimethyl ether-steam reforming hydrogen manufacturing is carried out in two steps, promptly dme is hydrolyzed into methyl alcohol, methyl alcohol earlier and becomes hydrogen rich off gas (H through steam reforming again 2And CO 2).Therefore the dimethyl ether-steam reforming catalyzer generally is made up of two kinds of active ingredients of hydrolysis of catalysis dme and methanol steam reforming reaction.Chinese patent CN101822993A adopts by carried phospho-tungstic acid catalyzer and Cu/ZnO/Al 2O 3The dual-function catalyst that commercial methanol steam reforming catalyzer is composited carries out dimethyl ether-steam reforming, obtained higher reaction preference, but the dimethyl ether conversion rate is very low.Chinese patent CN101396663A discloses γ-Al with Cu-Mn-X/ 2O 3(X is one or more among Al, Zn, Fe, Zr, the La) is used for the dimethyl ether-steam reforming reaction.U.S. Pat 6361757 discloses with Cu, Fe, Co, Pb, Pt, Ir, Rh, Ni etc. as active ingredient, and aluminum oxide, silica gel, molecular sieve etc. are used for dimethyl ether-steam hydrogen manufacturing as carrier.Can find out that in the prior art of dimethyl ether-steam reforming catalyzer, the main active ingredient great majority with reforming function are copper and other metals.The dimethyl ether-steam reforming catalyzer that MOX is complementary as reforming activity component and modified aluminas rarely has open.Compare with noble metal-based catalysts with the copper base of metal mold, metal oxide catalyst have the reduction of need not before the use, not easy-sintering, the preparation method is simple and advantage such as cheap.
Summary of the invention
The object of the present invention is to provide a kind of catalysis process of new dimethyl ether-steam reforming hydrogen manufacturing; Method itself be to provide a kind of with MOX as the dual-function catalyst of reforming activity component with modified aluminas coupling with hydrolysis function, and the technical scheme that is used for dimethyl ether-steam reforming hydrogen manufacturing that is determined by this catalyst themselves character.
For realizing above-mentioned purpose, the inventor furthers investigate, and finds to compare with preparing hydrogen by reforming methanol, and the dme reformation hydrogen production is the cascade reaction (CH that comprises hydrolysis and reformation 3OCH 3+ H 2O → 2CH 3OH, CH 3OH+H 2O → 3H 2+ CO 2), hydrolysis is carried out on acid sites, reforms and on the methanol steam reforming catalyzer, carries out.Therefore realize that characteristic of the present invention is the dual-function catalyst of invention hydrolysis and reformation, and two active site existence synergies, in other words, be the intermediate materials that forms in the heart in, shift to another center subsequently.The inventor finds, coprecipitation method or pickling process through routine are prepared into ZnM with zinc and another kind of metal xO y(x>=1, y>=2, x, y ∈ N) structure is scattered in ZnM with ZnO again xO yOn, two concrete instances are that zinc, chromium are prepared into sosoloid (ZnCr 2O 4) or zinc, aluminium is prepared into spinel (ZnAl 2O 4), again ZnO is scattered in ZnCr 2O 4Or ZnAl 2O 4On, reaction has very high activity to methanol steam reforming; Activated alumina has the acid site and distributes, and can impel dme to be hydrolyzed into methyl alcohol, but because the existence and the higher surface area (～290m of its weak acid position 2/ g) with little pore volume (～0.3cm 3/ g), when impelling dme to be hydrolyzed into methyl alcohol, generate lower carbon number hydrocarbons, generate and reduce methyl alcohol (or hydroxyl).TiO 2Specific surface is little, and anti-carbon is with Al 2O 3Compound back surface-area is moderate with the acid amount, and the acid site distributes and concentrates on middle strong acidic site, as hydrolyst, with ZnO-ZnM 2O 4The reforming activity temperature is coincide, and has high reactivity.
The present invention is based on above-mentioned research and resolve and propose following technical scheme:
A kind of method of dimethyl ether-steam reforming hydrogen manufacturing is a raw material with dme and water, and in fixed-bed reactor, temperature of reaction is 380-470 ℃, and reaction velocity is 1000-22000h -1, water and dme mol ratio are under the 3-7 condition, raw material dme and vaporous water mix, after preheating 100-380 ℃ with ZnO-ZnM 2O 4/ TiO 2-Al 2O 3The dual-function catalyst contact generates the reformed gas that is rich in hydrogen.
Wherein, ZnO-ZnM 2O 4/ TiO 2-Al 2O 3Element M is selected from a kind of among Cr, the Al etc. in the dual-function catalyst, when element M is selected from Cr, Al respectively, and ZnO and ZnCr 2O 4Mass ratio be 2-24, be preferably 2-11; ZnO and ZnAl 2O 4Mass ratio be＞0 to 10, be preferably＞0 to 5; TiO 2With Al 2O 3Mass ratio be 0.03-0.2, be preferably 0.03-0.15; ZnM 2O 4With TiO 2-Al 2O 3Mass ratio is 0.33-5, is preferably 1-5.
Related dimethyl ether-steam reforming catalyzer ZnO-ZnM in the inventive method 2O 4/ TiO 2-Al 2O 3Adopt following method to prepare ZnO-ZnM 2O 4Adopt conventional coprecipitation method or immersion process for preparing by required mass ratio, wherein, independent phase ZnO disperses available back pickling process or is preparing ZnM 2O 4The time directly excessive; TiO 2-Al 2O 3Adopt deposition-sedimentation to prepare by required mass ratio.With the ZnO-ZnM that makes 2O 4With TiO 2-Al 2O 3Catalyst fines is pressed required mass ratio through the mechanical mill thorough mixing; And make catalyzer of the present invention through re-baking in 400-600 ℃; The granularity of this catalyzer, i.e. moulding can be selected according to reactor size and processing condition, and reactor drum can be fixed bed or fluidized-bed; Catalyzer is packed into does not need reduction activation behind the reactor drum, under isothermal condition or adiabatic condition, directly carries out the dimethyl ether-steam reforming hydrogen production reaction.Temperature of reaction is preferably 400-470 ℃, and water mixes with dme after vaporization, and both mol ratios are 3.5-7, and reaction pressure is a normal pressure.
What need explanation is, reaches the catalyzer of preparation process gained according to the above ratio, wherein, and TiO 2-Al 2O 3Has the function that dme is hydrolyzed to methyl alcohol, ZnO-ZnM 2O 4Have catalytic reforming methanol is the function of hydrogen.With separate dispersed phase ZnO and sosoloid ZnM 2O 4The zinc that form exists is the reformation active sites, sosoloid ZnM 2O 4The dual identity that possesses carrier and active ingredient, particularly importantly ZnM 2O 4Structure has temperature tolerance, stabilizing catalyst activity effect well.
Adopt technical scheme of the present invention, with the complex metal oxides ZnO-Cr of cheapness 2O 3/ TiO 2-Al 2O 3Or ZnO-Al 2O 3/ TiO 2-Al 2O 3As the dimethyl ether-steam reforming catalyzer, temperature of reaction is 380-470 ℃, and reaction velocity is 1000-22000h -1, water and dme mol ratio are under the 3-7 condition, and the dimethyl ether conversion rate can reach 100%, and the CO selectivity is low, and denier methane generates.At 420 ℃ of temperature of reaction, H 2O/DME=4, gas phase air speed 5900h -1Under the condition, catalyst activity (DME transformation efficiency＞95%) and products distribution (H 2=74-75vol% CO=1.4-1.5vol%) did not change in 50 hours, possessed prospects for commercial application.
Through embodiment the present invention is done further elaboration below, but do not limit the scope of the invention.
Embodiment 1
(1) according to zinc, chromium solid solution (ZnCr 2O 4) stoichiometric ratio required nitrate salt be made into the positively charged ion total concn 1M aqueous solution and 1M ammoniacal liquor and flow in settling bath, keep that solution temperature is 50-60 ℃ in the settling bath, pH=7; Deposition is complete, ageing 2 hours, centrifuge washing; 100 ℃ of oven dry, 500 ℃ of roastings 4 hours are prepared into ZnCr 2O 4It is subsequent use to be made into the 2mol/L concentration of aqueous solution with zinc nitrate.Get prepared ZnCr 2O 4Powder is with zinc nitrate aqueous solution dipping ZnO and ZnCr 2O 4Mass ratio be 24,90 ℃ of oven dry, 500 ℃ of roastings 4 hours are prepared into ZnO-ZnCr 2O 4Catalyzer.
(2) choose activated alumina and put into settling bath, according to TiO 2With Al 2O 3Mass ratio be 0.1, the soluble salt of getting required titanium is made into the aqueous solution, stirs down with 1M Ti (SO 4) 2The aqueous solution and 1M ammoniacal liquor also flow in settling bath, control settling bath in solution temperature 50-60 ℃, pH=7-8.Precipitin reaction is complete, and ageing, washing are to there not being SO 4 2-, 100 ℃ of oven dry, 500 ℃ of roastings 4 hours are prepared into TiO 2-Al 2O 3Hydrolyst.
(3) with the ZnO-ZnCr that makes 2O 4And TiO 2-Al 2O 3Catalyst powder is that 2 mechanically mixing are even by mass ratio, 500 ℃ of roastings 3 hours.
(4) with the ZnO-Cr that makes 2O 3/ TiO 2-Al 2O 3The catalyst powder compressing tablet sieves into the 40-60 order, puts into the fixed-bed micro-reactor that channel diameter is 1.5mm, 380 ℃ of temperature of reaction, and water and dme mol ratio are 5, raw material gets into earlier reactor drum, gas phase air speed 1000h behind carburetion system -1Normal pressure is reaction down, dimethyl ether conversion rate 98.49%, H 2Be respectively 74.47%, 1.49% with the CO volumetric molar concentration.
Embodiment 2
According to each procedure of embodiment 1, difference is, changes ZnO and ZnCr among the embodiment 1 (1) 2O 4Mass ratio be 2, change among the embodiment 1 (4) 440 ℃ of temperature of reaction, gas phase air speed 7900h -1, dimethyl ether conversion rate 99.75%, H 2, the CO volumetric molar concentration is respectively 74.45%, 1.73%.
Embodiment 3
According to each procedure of embodiment 2, difference is, changes TiO among the embodiment 1 (2) 2With Al 2O 3Mass ratio be 0.03,400 ℃ of maturing temperatures, dimethyl ether conversion rate 99.71%, H 2, the CO volumetric molar concentration is respectively 74.41%, 1.67%.
Embodiment 4
According to each procedure of embodiment 1, difference is, changes TiO among the embodiment 1 (2) 2With Al 2O 3Mass ratio be 0.2,600 ℃ of maturing temperatures, dimethyl ether conversion rate 98.92%, H 2, the CO volumetric molar concentration is respectively 74.54%, 1.29%.
Embodiment 5
According to each procedure of embodiment 2, difference is that only changing temperature of reaction is 430 ℃, dimethyl ether conversion rate 90.89%, H 2, the CO volumetric molar concentration is respectively 74.42%, 1.51%.
Embodiment 6
According to each procedure of embodiment 5, difference is that only changing temperature of reaction is 470 ℃, gas phase air speed 22000h -1, dimethyl ether conversion rate 95.98%, H 2, the CO volumetric molar concentration is respectively 74.10%, 2.22%.
Embodiment 7
According to each procedure of embodiment 2, difference is that only changing temperature of reaction is 430 ℃, and water and dme mol ratio are 3, dimethyl ether conversion rate 96.40%, H 2, the CO volumetric molar concentration is respectively 73.55%, 3.46%.
Embodiment 8
According to each procedure of embodiment 2, difference is that water and dme mol ratio are 7, dimethyl ether conversion rate 90.86%, H 2, the CO volumetric molar concentration is respectively 74.66%, 0.93%.
Embodiment 9
According to each procedure of embodiment 2, difference is, only changes ZnO-Cr 2O 3And TiO 2-Al 2O 3Mass ratio be 0.33, temperature of reaction is 460 ℃, dimethyl ether conversion rate 99.07%, H 2, the CO volumetric molar concentration is respectively 73.83%, 2.20%.
Embodiment 10
According to each procedure of embodiment 2, difference is, only changes ZnO-ZnCr 2O 4And TiO 2-Al 2O 3Mass ratio be 5, temperature of reaction is 440 ℃, dimethyl ether conversion rate 95.64%, H 2, the CO volumetric molar concentration is respectively 74.31%, 1.69%.
Embodiment 11
According to each procedure of embodiment 2, difference is that only changing temperature of reaction is 450 ℃, dimethyl ether conversion rate 100%, H 2, the CO volumetric molar concentration is respectively 74.27%, 1.91%.
Embodiment 12
At first, preparation ZnO-Al 2O 3According to zinc, aluminium in spinel (ZnAl 2O 4) stoichiometric ratio required nitrate salt be made into the positively charged ion total concn 1M aqueous solution and 1M ammoniacal liquor and flow in settling bath, keep vs pH=8 deposition fully, ageing 30min, filtering and washing, 100 ℃ of oven dry, 500 ℃ of roastings 4 hours are prepared into ZnAl 2O 4, with the zinc nitrate aqueous solution dipping ZnAl of embodiment 1 2O 4Powder satisfies ZnO and ZnAl 2O 4Mass ratio is 10,90 ℃ of oven dry, and 500 ℃ of roastings 4 hours are prepared into ZnO-ZnAl 2O 4Reforming catalyst.
Secondly, preparation TiO 2-Al 2O 3Choose activated alumina and put into settling bath, according to TiO 2With Al 2O 3Mass ratio be 0.1, the soluble salt of getting required titanium is made into the aqueous solution, stirs down with 1M Ti (SO 4) 2The aqueous solution and 1M ammoniacal liquor also flow in settling bath, control settling bath in solution temperature 50-60 ℃, pH=7-8.Precipitin reaction is complete, and ageing, washing are to there not being SO 4 2-, 100 ℃ of oven dry, 500 ℃ of roastings 4 hours are prepared into TiO 2-Al 2O 3Hydrolyst.
With the ZnO-ZnAl that makes 2O 4And TiO 2-Al 2O 3Catalyst powder is that 2 mechanically mixing are even by mass ratio, 500 ℃ of roastings 3 hours, the ZnO-Cr of gained 2O 3/ TiO 2-Al 2O 3The catalyst powder compressing tablet sieves into the 40-60 order, puts into fixed-bed micro-reactor, 440 ℃ of temperature of reaction, and water and dme mol ratio are 5, raw material gets into earlier reactor drum, gas phase air speed 6000h behind carburetion system -1Normal pressure is reaction down, dimethyl ether conversion rate 98.31%, H 2Be respectively 74.25%, 1.92% with the CO volumetric molar concentration.
Embodiment 13
Each procedure according to embodiment 12 only changes ZnO and ZnAl 2O 4Mass ratio be 0.001, dimethyl ether conversion rate 100%, H 2, the CO volumetric molar concentration is respectively 74.37%, 1.60%.
The inventive method dimethyl ether catalysis transformation efficiency reaches 100%, and the CO selectivity is low, no methanation reaction, and the Preparation of Catalyst cost is low, need not reduction and good stability, can be used for suitability for industrialized production.

Claims (7)

1. the method for a dimethyl ether-steam reforming hydrogen manufacturing, it is characterized in that: with dme and water is raw material, and in fixed-bed reactor, temperature of reaction is 380-470 ℃, and reaction velocity is 1000-22000h -1, water vapour and dme are the mixed of 3-7 with the mol ratio, are preheated to after the temperature of reaction and ZnO-ZnM 2O 4/ TiO 2-Al 2O 3The dual-function catalyst contact generates the reformed gas that is rich in hydrogen; ZnO-ZnM in the said dual-function catalyst 2O 4With TiO 2-Al 2O 3The mass ratio of two kinds of composite reactive components is 0.33-5.
2. according to the method for the said dimethyl ether-steam reforming hydrogen manufacturing of claim 1, it is characterized in that: said dual-function catalyst ZnO-ZnM 2O 4/ TiO 2-Al 2O 3In element M be selected from a kind of among Cr, the Al.
3. according to the method for the said dimethyl ether-steam reforming hydrogen manufacturing of claim 1, it is characterized in that: ZnO and ZnCr 2O 4Mass ratio be 2-24; ZnO and ZnAl 2O 4Mass ratio be＞0 to 10; TiO 2With Al 2O 3Mass ratio be 0.03-0.2.
4. according to the method for the said dimethyl ether-steam reforming hydrogen manufacturing of claim 3, it is characterized in that: ZnO and ZnCr 2O 4Mass ratio be 2-11; ZnO and ZnAl 2O 4Mass ratio be＞0 to 5; TiO 2With Al 2O 3Mass ratio be 0.03-0.15.
5. according to the method for the said dimethyl ether-steam reforming hydrogen manufacturing of claim 1, it is characterized in that ZnO-ZnM 2O 4With TiO 2-Al 2O 3The mass ratio of two kinds of composite reactive components is 1-5.
6. according to the method for any said dimethyl ether-steam reforming hydrogen manufacturing of claim 1-6, it is characterized in that: said dual-function catalyst ZnO-ZnM 2O 4/ TiO 2-Al 2O 3Middle ZnO-ZnM 2O 4Be the active ingredient of catalysis methanol steam reforming, TiO 2-Al 2O 3Be the active ingredient of catalysis dme hydrolysis, after two components prepare respectively,, and, be used for the dimethyl ether-steam reforming hydrogen production reaction after the moulding in 400-600 ℃ of re-baking with Powdered thorough mixing.
7. according to the method for the said dimethyl ether-steam reforming hydrogen manufacturing of claim 1, it is characterized in that: temperature of reaction is 400-470 ℃, and water mixes with dme after gasification, and both mol ratios are 3.5-7, and reaction pressure is a normal pressure.
CN201110139959.XA 2011-05-25 2011-05-25 Method for reforming dimethyl ether water steam to generate hydrogen Expired - Fee Related CN102795598B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108927133A (en) * 2018-06-28 2018-12-04 华南理工大学 A kind of dimethyl ether-steam reforming catalyst and its hydrogen production process
CN112986047A (en) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 Method for measuring steam content in reformed gas and method for evaluating and measuring reforming fuel conversion rate

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CN101485983A (en) * 2009-02-17 2009-07-22 同济大学 Catalyst for hydrogen production from dimethyl ether-steam reforming and preparation method thereof
CN101612563A (en) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 The composite oxide catalysts of hydrogen production from methanol-steam reforming and preparation thereof and application
CN101822993A (en) * 2010-05-10 2010-09-08 华东理工大学 Preparation and application of dimethyl ether steam reformed hydrogen catalyst

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CN101396663A (en) * 2008-09-24 2009-04-01 同济大学 Catalyst capable of making hydrogen by dimethyl ether vapor reformation, preparation and use method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108927133A (en) * 2018-06-28 2018-12-04 华南理工大学 A kind of dimethyl ether-steam reforming catalyst and its hydrogen production process
CN108927133B (en) * 2018-06-28 2021-01-19 华南理工大学 Dimethyl ether steam reforming catalyst and hydrogen production method thereof
CN112986047A (en) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 Method for measuring steam content in reformed gas and method for evaluating and measuring reforming fuel conversion rate
CN112986047B (en) * 2019-12-12 2022-02-01 中国科学院大连化学物理研究所 Method for measuring steam content in reformed gas and method for evaluating and measuring reforming fuel conversion rate

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