CN101822993B - Preparation and application of dimethyl ether steam reformed hydrogen catalyst - Google Patents
Preparation and application of dimethyl ether steam reformed hydrogen catalyst Download PDFInfo
- Publication number
- CN101822993B CN101822993B CN2010101697645A CN201010169764A CN101822993B CN 101822993 B CN101822993 B CN 101822993B CN 2010101697645 A CN2010101697645 A CN 2010101697645A CN 201010169764 A CN201010169764 A CN 201010169764A CN 101822993 B CN101822993 B CN 101822993B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- dimethyl ether
- tungstic acid
- zno
- carried phospho
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a solid bifunctional catalyst and a preparation method and use thereof. The solid bifunctional catalyst is formed by compounding a supported phosphotungstic acid catalyst with a Cu/ZnO/Al2O3 commercial methanol steam reformed hydrogen catalyst. The invention also discloses a using method of the solid bifunctional catalyst in the process of dimethyl ether steam reforming hydrogen production.
Description
Technical field
The present invention relates to chemical industry and energy field, relate in particular to the preparation and the application of dimethyl ether steam reformed hydrogen catalyst.
Background technology
Hydrogen is as a kind of cleaning, efficient, the safe energy, is one of the most potential sustainable energy in this century.It is a kind of secondary energy sources, must utilize hydrogeneous raw material to produce through certain method.Current, the large-scale industry more than 90% comes from the conversion of fossil energies such as coal, oil and natural gas with hydrogen, and small-scale or the on-the-spot technology such as water electrolysis hydrogen producing, organic-fuel hydrogen manufacturing, preparing hydrogen by ammonia decomposition that mainly adopt with hydrogen.Dimethyl ether utilizes its hydrogen manufacturing just more and more to come into one's own as a kind of new energy carrier, and this is that non-corrosiveness and carcinogenic are a kind of industrial chemicals of environmental protection because of the dimethyl ether safety non-toxic.Dimethyl ether has easy compression, condensation, gasification, and with characteristics such as many polarity or non-polar solven dissolve each other, be widely used in aerosol goods propellant, freon alternative refrigerant, solvent etc. at present, also be used for the synthetic of other chemicals, purposes is very extensive.The saturated vapour pressure of dimethyl ether is lower than liquefied petroleum gas, can be as liquefied petroleum gas can, storage and transportation, and also more safer than liquefied gas.Therefore, realize a kind of comparatively ideal selection of on-the-spot hydrogen manufacturing on a small scale with the dimethyl ether beyond doubt for raw material hydrogen manufacturing.
At present; The hydrogen manufacturing mode that with the dimethyl ether is raw material mainly contains dimethyl ether steam reformed hydrogen, dimethyl ether partial oxidation reformation hydrogen production and dimethyl ether self-heating reforming hydrogen manufacturing etc.; Wherein, the dimethyl ether steam reformed hydrogen process has hydrogen output height, characteristics that reaction temperature is low, thereby most popular.It is generally acknowledged that the dimethyl ether steam reformed hydrogen reaction mechanism is: dimethyl ether carried out hydrolysis on acidic catalyst before this, was that the methyl alcohol that hydrolysis forms carries out steam reforming reaction then on metallic catalyst, produced hydrogen.Therefore, the dimethyl ether steam reformed hydrogen process adopts bifunctional catalyst mostly.In the dimethyl ether steam reformed hydrogen device like Chinese patent CN101177240A report, supportingly adopt ZSM-5 molecular sieve catalyst and the compound bifunctional catalyst of copper-based catalysts, but do not mentioned the direct catalytic effect of bifunctional catalyst.Chinese patent CN101396663A adopts Cu-Mn-X/ γ-Al
2O
3(X is one or more among Al, Zn, Fe, Zr, the La), as the dimethyl ether steam reformed hydrogen catalyst for reaction, wherein, γ-Al
2O
3Have hydrolysing activity, Cu-Mn-X has dehydrogenation functionality, but the reaction temperature of the type catalyst is higher, and CO is arranged in the product.U.S. Pat 5837217 has been reported industrial ZSM-5 molecular sieve catalyst and methanol decomposition Cu-Zn-Al catalyst has been carried out mechanical mixture, process catalyst and be used for the dimethyl ether steam reformed hydrogen reaction, but catalytic activity is lower, and selectivity is not high yet.(Semelsberger T A, Ott K C, Borup R L, et al.Appl Catal B, 2006,65 (3-4): such as Semelsberger T A 291-300) with Cu/ZnO/Al
2O
3The same ZSM-5 of commercial methanol steam reforming catalyst, molecular sieve Y (m (Si)/m (Al)=2.5-140), γ-Al
2O
3And ZrO
2Carry out physical mixed etc. several kinds of solid acid catalysts, the catalyst activity of finding to contain ZSM-5 is higher, under 275 ℃ reforming temperature, the selectivity of hydrogen is reached more than 94%.
Can influence the service efficiency of hydrogen owing to the existence of impurity such as CO in the hydrogen; And cause catalyst poisoning in the hydrogen use; Therefore; The hydrogen application is high to the purity requirement of hydrogen, requires CO content to be lower than 10ppm like hydrogen fuel cell, and this just requires selected hydrogen production process high more good more to the selectivity of hydrogen.And problem such as at present dimethyl ether steam reformed hydrogen process ubiquity hydrogen selective is low.
Therefore, this area press for a kind of high selectivity is provided catalyst applications in the process of dimethyl ether steam reformed hydrogen.
Summary of the invention
The present invention aims to provide a kind of solid bifunctional catalyst and preparation method thereof.
Another object of the present invention provides the method for using of said catalyst in the dimethyl ether steam reformed hydrogen process.
In first aspect of the present invention, a kind of solid bifunctional catalyst is provided, contain carried phospho-tungstic acid catalyst and Cu/ZnO/Al in the described catalyst
2O
3The methanol steam reforming catalyst; Carried phospho-tungstic acid catalyst and Cu/ZnO/Al in the said catalyst
2O
3The weight ratio of methanol steam reforming catalyst is 5: 1-1: 5.
Described carried phospho-tungstic acid catalyst is made up of carrier and phosphotungstic acid, and in the gross weight of carried phospho-tungstic acid catalyst, the phosphotungstic acid weight percentage is 5-50%; Described carrier is activated alumina, silica, titanium oxide, molecular sieve, active carbon.
In second aspect of the present invention, a kind of preparation method of aforesaid solid bifunctional catalyst provided by the invention is provided, described method comprises step: with carried phospho-tungstic acid catalyst and Cu/ZnO/Al
2O
3The methanol steam reforming catalyst is compound, obtains aforesaid solid bifunctional catalyst provided by the invention.
Load in order or mechanical mixture described compound comprising.Described filling in order is meant the carried phospho-tungstic acid catalyst granules is filled in solid reactor gas access end, with Cu/ZnO/Al
2O
3Methanol steam reforming catalyst particle is filled in the gas reactor port of export, and both directly contact the middle part; Described mechanical mixture is with carried phospho-tungstic acid catalyst fines and Cu/ZnO/Al
2O
3Methanol steam reforming catalyst powder is through mechanical agitation or grind and to mix both are dried.
In another preference, described preparation method comprises step:
A. phosphotungstic acid and water are mixed, dissolve, obtain Salkowski's solution;
B. the Salkowski's solution that carrier and step a is obtained mixes, stirs, and obtains sample 1;
C. sample 1 is placed on 120 ℃ and carries out drying, be warming up to 200 ℃ continue dryings after, cooling obtains the carried phospho-tungstic acid catalyst; With
D. the carried phospho-tungstic acid catalyst and the Cu/ZnO/Al that step c are obtained
2O
3The methanol steam reforming catalyst is compound, obtains aforesaid solid bifunctional catalyst provided by the invention.
In the third aspect of the invention, a kind of purposes of aforesaid solid bifunctional catalyst provided by the invention is provided, be used for the dimethyl ether steam reformed hydrogen catalytic process.
In fourth aspect of the present invention, a kind of dimethyl ether steam reformed hydrogen method is provided, described method comprises step:
(1) gaseous mixture with dimethyl ether and water vapour reacts through the fixed bed reactors that are filled with aforesaid solid bifunctional catalyst provided by the invention, obtains hydrogen.
The mol ratio of dimethyl ether and water vapour is 2 in the said gaseous mixture: 1-1: 5.
The air speed of the gaseous mixture of said dimethyl ether and water vapour is 500-25000ml/ (gcath); Carry out under said 0.5-2.5atm of being reflected at and the 180-350 ℃ condition.
In view of the above, the catalyst applications that the invention provides a kind of high selectivity is in the process of dimethyl ether steam reformed hydrogen.
The specific embodiment
The inventor is surprised to find that carried phospho-tungstic acid catalyst and Cu/ZnO/Al through extensive and deep research
2O
3After commercial methanol-water steaming reforming catalyst is compound, form the solid bifunctional catalyst, can be applicable in the dimethyl ether steam reformed hydrogen process, reaction selectivity is very high, reach more than 99.9%, and reactivity is also better.
The solid bifunctional catalyst
The invention provides a kind of solid bifunctional catalyst, contain carried phospho-tungstic acid catalyst and Cu/ZnO/Al
2O
3Methanol steam reforming catalyst, carried phospho-tungstic acid catalyst have solid acid makes dimethyl ether be hydrolyzed to the function of methyl alcohol, Cu/ZnO/Al
2O
3Commercial catalysts has the methanol steam reforming function.
Described carried phospho-tungstic acid catalyst is made up of carrier and active component phosphotungstic acid, has solid acid catalyst and makes dimethyl ether be hydrolyzed to the function of methyl alcohol.As used herein, " carrier " is meant the porous solid material that is used for the dispersed catalyst active component, such as but not limited to activated alumina, silica, titanium oxide, molecular sieve, active carbon, is preferably silica, HTS.In the gross weight of carried phospho-tungstic acid catalyst, wherein the percentage by weight of phosphotungstic acid is 5-50wt%, preferably is 10-40wt%, more preferably is 8.5-36.5wt%.
Described Cu/ZnO/Al
2O
3The methanol steam reforming catalyst can be through well known in the art, through the Cu/ZnO/Al of conventional commercial channel acquisition
2O
3The methanol steam reforming catalyst is called " Cu/ZnO/Al in this article
2O
3Commercial methanol steam reforming catalyst ".There are Nanjing catalyst plant, Chuanhua Co., Ltd.'s catalyst plant etc. in manufacturer well known in the art.
Solid bifunctional catalyst provided by the invention, carried phospho-tungstic acid catalyst and Cu/ZnO/Al
2O
3Commercial both weight ratios of methanol steam reforming catalyst are 5: 1-1: 5; Be preferably 3: 1-1: 3.
Solid bifunctional catalyst provided by the invention is by carried phospho-tungstic acid catalyst and Cu/ZnO/Al
2O
3Commercial methanol steam reforming catalyst is composited, the described compound mode of filling in order or the mode of mechanical mixture of adopting.
The described mode of loading in order is meant the carried phospho-tungstic acid catalyst granules is filled in the gas reactor arrival end, with Cu/ZnO/Al
2O
3Commercial methanol steam reforming catalyst particle is filled in the gas reactor port of export, and both directly contact the middle part.The mode of described mechanical mixture is meant carried phospho-tungstic acid catalyst fines and Cu/ZnO/Al
2O
3Commercial methanol steam reforming catalyst powder, through mechanical agitation or grind and mix both are dried, compressing tablet then uses after being broken into moulding such as particle again.
Described carried phospho-tungstic acid catalyst can prepare through method well known in the art, such as but not limited to immersion process for preparing.Preparation process is following:
(1) phosphotungstic acid is at room temperature mixed with water, stir, dissolve fully to phosphotungstic acid, be made into Salkowski's solution;
(2) Salkowski's solution that carrier and step (1) is obtained mixes, and fully stirs, and obtains sample 1;
(3) sample 1 that step (2) is obtained is put into 120 ℃ of drying boxes, and keeps 12h, and the program with 5 ℃/min makes drying box rise to 200 ℃ then, and keeps 10h; Naturally after the cooling, obtain the carried phospho-tungstic acid catalyst.
In a preference of the present invention, described carried phospho-tungstic acid catalyst prepares through following method:
(1) takes by weighing the 0.5-4.5g phosphotungstic acid and put into beaker, at room temperature add the 8g deionized water, stir, dissolve fully to phosphotungstic acid, be made into the 5.9-36.0wt% Salkowski's solution;
(2) the 6g carrier that weighs up is added in the beaker of step (1), and fully stir; With
(3) sample that step (2) is obtained is put into 120 ℃ of drying boxes, and keeps 12h, and the program with 5 ℃/min makes drying box rise to 200 ℃ then, and keeps 10h.Naturally after the cooling, promptly get 7.7-42.9wt% carried phospho-tungstic acid catalyst.
Solid bifunctional catalyst provided by the invention can be used for the dimethyl ether steam reformed hydrogen catalytic reaction.
The dimethyl ether steam reformed hydrogen catalysis process
Dimethyl ether steam reformed hydrogen catalytic reaction process of the present invention carries out in fixed bed reactors, and dimethyl ether is a gas, and water is mixed into reactor with dimethyl ether after 250 ℃ of heating vaporizations.Be filled with solid bifunctional catalyst provided by the invention in the reactor.The gaseous mixture of dimethyl ether and water vapour is reacted through the fixed bed reactors that are filled with solid bifunctional catalyst provided by the invention, obtain hydrogen.
Dimethyl ether is 2 with the mol ratio of mixing of water vapour: 1-1: 5, be preferably 1: 1-1: 5, more preferably 1: 1-1: 4.
Be reflected under the normal pressure 0.5-2.5atm and carry out; Reaction temperature is 180-350 ℃, preferred 200-280 ℃; The air speed of mist (dimethyl ether and water vapour) (referring to the volume number that every gram catalyst per hour flows through) is 500-25000ml/ (gcath), is preferably 1000-20000ml/ (gcath), more preferably 2000-20000ml/ (gcath).
As used herein, " fixed bed reactors " and " reactor " can exchange use, all are meant the fixed bed reactors that are filled with solid catalyst.
As used herein, " atm " is meant standard atmospheric pressure, 1atm=0.101325MPa.
The above-mentioned characteristic that the present invention mentions, or the characteristic that embodiment mentions can combination in any.All characteristics that this case specification is disclosed can with any composition forms and usefulness, each characteristic that is disclosed in the specification can anyly provide the alternative characteristics of identical, impartial or similar purpose to replace.Therefore removing has special instruction, the characteristic that is disclosed to be merely the general example of equalization or similar features.
Major advantage of the present invention is:
1, the catalyst reaction selectivity is high, and is active good, can be used in situ preparation hydrogen.
2, dimethyl ether can react with water under normal pressure and lower temperature, and catalysis generates hydrogen.
3, method for preparing catalyst is simple, and raw material is easy to get.
4, reaction raw materials is nontoxic, inexpensive, and reaction unit is simple.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example is usually according to the normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage, ratio, ratio or umber by weight.
Unit in the percent weight in volume among the present invention is well-known to those skilled in the art, for example is meant the weight of solute in 100 milliliters solution.
Unless otherwise defined, employed all specialties are identical with the meaning that scientific words and one skilled in the art are familiar with in the literary composition.In addition, any with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
The Cu/ZnO/Al that uses in embodiments of the present invention
2O
3Commercial methanol steam reforming catalyst, model XNC-98 is provided by the Nanjing catalyst plant.
In an embodiment of the present invention, adopt gas chromatography (sky, Hong Kong U.S. chromatographic apparatus GC789OF of company gas chromatograph) on-line analysis reaction afterproduct to form, be two chromatographic column double air road systems; Carrier gas is an Ar gas; Flow is 40ml/min, adopts the TCD detector, and detector temperature is 50 ℃; Bridge stream is 80mA, analyzes H with the 5A molecular sieve packed column
2, CO and CH
4Deng composition, column temperature is 50 ℃, GDX101 packed column Analysis for CO
2, composition such as dimethyl ether and methyl alcohol, column temperature is 50 ℃-180 ℃, heating rate is 10 ℃/min.
With dimethyl ether conversion rate and hydrogen selectivity as the catalyst performance evaluation index, definition as follows:
Embodiment 1
The solid bifunctional catalyst prepares I
Adopt immersion process for preparing carried phospho-tungstic acid catalyst.Prepare 11.5g 30.0wt% Salkowski's solution earlier.6g silicon oxide powder (the May 4th chemical reagent Co., Ltd provides by Shanghai) is mixed with above-mentioned solution, dry then, obtain 36.5wt% carried phospho-tungstic acid catalyst fines after the cooling.With getting 40-60 order particle 1.5g after gained catalyst compressing tablet, the fragmentation, with the Cu/ZnO/Al of same 40-60 order 1.5g
2O
3Commercial methanol steam reforming catalyst, the mode by loading in order in the fixed bed reactors of packing into, promptly gets the solid bifunctional catalyst.
Embodiment 2
Dimethyl ether steam reformed hydrogen catalytic reaction process I
In the described reactor that is filled with the solid bifunctional catalyst of embodiment 1, feed earlier the 10vol%H of 250ml/min flow
2/ Ar gaseous mixture, reactor heating furnace be by the speed temperature programming to 280 of 3 ℃/min ℃, and keep 4h.Close H then
2/ Ar gaseous mixture; Feed the gaseous mixture of dimethyl ether and water vapour (mol ratio is 1: 3); Be to react under the condition of 20000ml/ (gcath) in normal pressure (1.5atm), air speed, detect gaseous product and form that calculating the dimethyl ether conversion rate is 23.9%; Hydrogen selective is 99.9%, does not detect CO and CH
4Existence.
Embodiment 3
The solid bifunctional catalyst prepares II
Adopt earlier immersion process for preparing 25.0wt% carried phospho-tungstic acid catalyst, carrier is HTS (building long catalyst Co., Ltd by the Hunan provides).Cu/ZnO/Al with gained 1.5g catalyst and identical weight
2O
3Commercial methanol steam reforming catalyst carries out mechanical agitation to be mixed, and gets 40-60 order particle 2.0g then after compressing tablet, the fragmentation and packs in the fixed bed reactors, promptly gets the solid bifunctional catalyst.
Embodiment 4
Dimethyl ether steam reformed hydrogen catalytic reaction process II
In the described reactor that is filled with the solid bifunctional catalyst of embodiment 3, feed earlier the 10vol%H of 250ml/min flow
2/ Ar gaseous mixture, reactor heating furnace be by the speed temperature programming to 280 of 3 ℃/min ℃, and keep 4h.Naturally be cooled to 250 ℃ then, close H
2/ Ar gaseous mixture; Feed the gaseous mixture of dimethyl ether and water vapour (mol ratio is 1: 3); Be to react under the condition of 4000ml/ (gcath) in normal pressure (1.5atm), air speed, detect gaseous product and form that calculating the dimethyl ether conversion rate is 53.5%; Hydrogen selective is 99.4%, does not detect CO and CH
4Existence.
Embodiment 5
The solid bifunctional catalyst prepares III
Adopt immersion process for preparing 20.0wt% carried phospho-tungstic acid catalyst earlier, carrier is titanium dioxide (being provided by Chemical Reagent Co., Ltd., Sinopharm Group).Cu/ZnO/Al with gained 4.5g catalyst and 1.5g
2O
3Commercial methanol steam reforming catalyst carries out mechanical lapping to be mixed, and gets 40-60 order particle 2.0g then after compressing tablet, the fragmentation and packs in the fixed bed reactors, promptly gets the solid bifunctional catalyst.
Embodiment 6
Dimethyl ether steam reformed hydrogen catalytic reaction process III
In the described reactor that is filled with the solid bifunctional catalyst of embodiment 5, feed earlier the 10vol%H of 250ml/min flow
2/ Ar gaseous mixture, reactor heating furnace be by the speed temperature programming to 280 of 3 ℃/min ℃, and keep 4h.Close H then
2/ Ar gaseous mixture; Feed the gaseous mixture of dimethyl ether and water vapour (mol ratio is 1: 1); Be to react under the condition of 2000ml/ (gcath) in normal pressure (0.5atm), air speed, detect gaseous product and form that calculating the dimethyl ether conversion rate is 7.4%; Hydrogen selective is 99.9%, does not detect CO and CH
4Existence.
Embodiment 7
The solid bifunctional catalyst prepares IV
Adopt immersion process for preparing 8.5wt% carried phospho-tungstic acid catalyst earlier, carrier is active carbon (being provided by Chemical Reagent Co., Ltd., Sinopharm Group).Cu/ZnO/Al with gained 1.5g catalyst and 4.5g
2O
3Commercial methanol steam reforming catalyst carries out mechanical lapping to be mixed, and gets 40-60 order particle 2.0g then after compressing tablet, the fragmentation and packs in the fixed bed reactors, promptly gets the solid bifunctional catalyst.
Embodiment 8
Dimethyl ether steam reformed hydrogen catalytic reaction process IV
In the described reactor that is filled with the solid bifunctional catalyst of embodiment 7, feed earlier the 10vol%H of 250ml/min flow
2/ Ar gaseous mixture, reactor heating furnace be by the speed temperature programming to 280 of 3 ℃/min ℃, and keep 4h.Naturally be cooled to 200 ℃ then, close H
2/ Ar gaseous mixture; Feed the gaseous mixture of dimethyl ether and water vapour (mol ratio is 1: 5); Be to react under the condition of 10000ml/ (gcath) in normal pressure (2.5atm), air speed, detect gaseous product and form that calculating the dimethyl ether conversion rate is 11.7%; Hydrogen selective is 99.9%, does not detect CO and CH
4Existence.
Comparative Examples 1
Directly get 40-60 purpose Cu/ZnO/Al
2O
3Commercial methanol steam reforming catalyst 2.0g in the fixed bed reactors of packing into, feeds the 10vol%H of 250ml/min flow
2/ Ar gaseous mixture, reactor heating furnace be by the speed temperature programming to 280 of 3 ℃/min ℃, and keep 4h.Naturally be cooled to 250 ℃ then, close H
2/ Ar gaseous mixture; Feed the gaseous mixture of dimethyl ether and water vapour (mol ratio is 1: 3); Be to react under the condition of 4000ml/ (gcath) in normal pressure (1.5atm), air speed, detect gaseous product and form that calculating the dimethyl ether conversion rate is 1.2%; Hydrogen selective is 45.6%, detects a large amount of CO and CH
4Existence.
Comparative Examples 2
Get the Cu/ZnO/Al of 1.5g HTS and identical weight
2O
3Commercial methanol steam reforming catalyst carries out mechanical agitation to be mixed, and gets 40-60 order particle 2.0g then after compressing tablet, the fragmentation, in the fixed bed reactors of packing into, feeds the 10vol%H of 250ml/min flow
2/ Ar gaseous mixture, reactor heating furnace be by the speed temperature programming to 280 of 3 ℃/min ℃, and keep 4h.Naturally be cooled to 250 ℃ then, close H
2/ Ar gaseous mixture; Feed the gaseous mixture of dimethyl ether and water vapour (mol ratio is 1: 3); Be to react under the condition of 4000ml/ (gcath) in normal pressure (1.5atm), air speed, detect gaseous product and form that calculating the dimethyl ether conversion rate is 0.7%; Hydrogen selective is 50.1%, detects a large amount of CO and CH
4Existence.
The above is merely preferred embodiment of the present invention; Be not in order to limit essence technology contents scope of the present invention; Essence technology contents of the present invention is broadly to be defined in the claim scope of application, and if any technological entity or method that other people accomplish are defined identical with the claim scope of application; Also or a kind of change of equivalence, all will be regarded as and be covered by among this claim scope.
Claims (9)
1. a solid bifunctional catalyst that is used for the dimethyl ether steam reformed hydrogen catalytic process is characterized in that, contains carried phospho-tungstic acid catalyst and Cu/ZnO/Al in the described catalyst
2O
3The methanol steam reforming catalyst; Carried phospho-tungstic acid catalyst and Cu/ZnO/Al in the said catalyst
2O
3The weight ratio of methanol steam reforming catalyst is 5: 1-1: 5;
Described carried phospho-tungstic acid catalyst is made up of carrier and phosphotungstic acid, and in the gross weight of carried phospho-tungstic acid catalyst, the phosphotungstic acid weight percentage is 5-50%; Described carrier is activated alumina, silica, titanium oxide, molecular sieve or active carbon.
2. the preparation method of a solid bifunctional catalyst as claimed in claim 1 is characterized in that, described method comprises step: with carried phospho-tungstic acid catalyst and Cu/ZnO/Al
2O
3The methanol steam reforming catalyst is compound, obtains solid bifunctional catalyst as claimed in claim 1.
3. preparation method as claimed in claim 2 is characterized in that, load in order or mechanical mixture described compound comprising.
4. preparation method as claimed in claim 3 is characterized in that, described filling in order is meant the carried phospho-tungstic acid catalyst granules is filled in solid reactor gas access end, with Cu/ZnO/Al
2O
3Methanol steam reforming catalyst particle is filled in the gas reactor port of export, and both directly contact the middle part; Described mechanical mixture is with carried phospho-tungstic acid catalyst fines and Cu/ZnO/Al
2O
3Methanol steam reforming catalyst powder is through mechanical agitation or grind and to mix both are dried.
5. preparation method as claimed in claim 2 is characterized in that, described preparation method comprises step:
A. phosphotungstic acid and water are mixed, dissolve, obtain Salkowski's solution;
B. the Salkowski's solution that carrier and step a is obtained mixes, stirs, and obtains sample 1;
C. sample 1 is placed on 120 ℃ and carries out drying, be warming up to 200 ℃ continue dryings after, cooling obtains the carried phospho-tungstic acid catalyst; With
D. the carried phospho-tungstic acid catalyst and the Cu/ZnO/Al that step c are obtained
2O
3The methanol steam reforming catalyst is compound, obtains solid bifunctional catalyst as claimed in claim 1.
6. the purposes of a solid bifunctional catalyst as claimed in claim 1 is characterized in that, is used for the dimethyl ether steam reformed hydrogen catalytic process.
7. a dimethyl ether steam reformed hydrogen method is characterized in that, described method comprises step:
(1) gaseous mixture with dimethyl ether and water vapour reacts through the fixed bed reactors that are filled with solid bifunctional catalyst as claimed in claim 1, obtains hydrogen.
8. method as claimed in claim 7 is characterized in that, the mol ratio of dimethyl ether and water vapour is 2 in the said gaseous mixture: 1-1: 5.
9. method as claimed in claim 9 is characterized in that, the air speed of the gaseous mixture of dimethyl ether and water vapour is 500-25000ml/ (gcat.h); Carry out under said 0.5-2.5atm of being reflected at and the 180-350 ℃ condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101697645A CN101822993B (en) | 2010-05-10 | 2010-05-10 | Preparation and application of dimethyl ether steam reformed hydrogen catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101697645A CN101822993B (en) | 2010-05-10 | 2010-05-10 | Preparation and application of dimethyl ether steam reformed hydrogen catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101822993A CN101822993A (en) | 2010-09-08 |
| CN101822993B true CN101822993B (en) | 2012-07-25 |
Family
ID=42687281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101697645A Expired - Fee Related CN101822993B (en) | 2010-05-10 | 2010-05-10 | Preparation and application of dimethyl ether steam reformed hydrogen catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101822993B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794166B (en) * | 2011-05-25 | 2014-02-26 | 中国科学院大连化学物理研究所 | Dimethyl ether (DME) steam reforming hydrogen production catalyst and preparation and application thereof |
| CN102795598B (en) * | 2011-05-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Method for reforming dimethyl ether water steam to generate hydrogen |
| CN103157474A (en) * | 2011-12-09 | 2013-06-19 | 华东理工大学 | Supported solid catalyst for heterogeneous Fenton system |
| CN102744070A (en) * | 2012-05-14 | 2012-10-24 | 上海交通大学 | Dimethyl ether carbon dioxide reforming hydrogen production catalyst, preparation method and use method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091513A (en) * | 2005-09-28 | 2007-04-12 | Toshiba Corp | Hydrogen generator and fuel cell system |
| 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 |
-
2010
- 2010-05-10 CN CN2010101697645A patent/CN101822993B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101822993A (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2415074C2 (en) | Production of hydrogen using electrochemical reforming and electrolyte regeneration | |
| Kugai et al. | Low-temperature reforming of ethanol over CeO 2-supported Ni-Rh bimetallic catalysts for hydrogen production | |
| CN101822993B (en) | Preparation and application of dimethyl ether steam reformed hydrogen catalyst | |
| CN104725229B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN105540588A (en) | Application of alpha-molybdenum carbide and metal-modified alpha-molybdenum carbide catalyst to reaction for preparing carbon monoxide through hydrogenation of carbon dioxide | |
| CN104725230B (en) | The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate | |
| CN104725224B (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN102674247B (en) | A kind of method of decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation and device | |
| CN101850272B (en) | Method for preparing hydrophobic catalyst by freezing molding | |
| El-Shafie et al. | Development of zeolite-based catalyst for enhancement hydrogen production from ammonia decomposition | |
| CN106807387A (en) | A kind of bifunctional catalyst for absorption enhancement hydrogen production by bio-oil steam reforming and preparation method thereof | |
| WO2012067222A1 (en) | Methanol production process | |
| CN104119207A (en) | Method for preparation of ethylene glycol by catalytic conversion of carbohydrate | |
| CN102489310A (en) | Composite oxide catalyst for auto-thermal reforming of biomass-oil for preparing hydrogen | |
| Badmaev et al. | Steam reforming of dimethoxymethane to hydrogen-rich gas for fuel cell feeding application. | |
| CN109369366B (en) | Method for preparing lactic acid by catalytic dehydrogenation of glycerol | |
| CN101619026B (en) | Synthesis method for continuously producing N,N-dimethyl cyclohexyl amine | |
| CN101391225A (en) | Catalyst for directly preparing dimethyl ether using carbon dioxide and use method thereof | |
| CN106076353A (en) | A kind of monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour | |
| CN110329992A (en) | Low-temperature methanol steam reforming catalyst for preparing hydrogen and preparation method thereof | |
| CN101538187A (en) | Application of nanometer ZSM-5 molecular sieve in reaction for preparing methanol by dimethyl ether catalysis and hydrolyzation | |
| Dongmei et al. | Steam reforming of dimethyl ether over coupled catalysts of CuO-ZnO-Al2O3-ZrO2 and solid-acid catalyst | |
| JP2006521990A (en) | Method for producing a hydrogen-rich stream | |
| Yoo et al. | Synthesis of dimethyl ether from syngas obtained by coal gasification | |
| CN102649685B (en) | The method of barkite high efficiency production ethylene glycol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120725 |