CN102872867B - Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst - Google Patents
Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst Download PDFInfo
- Publication number
- CN102872867B CN102872867B CN201210403330.6A CN201210403330A CN102872867B CN 102872867 B CN102872867 B CN 102872867B CN 201210403330 A CN201210403330 A CN 201210403330A CN 102872867 B CN102872867 B CN 102872867B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- steam reforming
- methanol
- cnt
- hydrogen production
- 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 catalyst used for hydrogen production by methanol steam reforming and a preparation method of the catalyst and relates to a catalyst. The catalyst refers to a carbon nanotube and scandium doubly-promoted coprecipitation type palladium-zinc based catalyst, the chemical formula of the catalyst is expressed as PdiZnjSck-x%CNT (carbon nanotube), wherein i, j and k in the formula refer to mole ratio coefficients of Pd, Zn and Sc respectively, x% refers to mass percent of CNT in the catalyst, and the catalyst comprises, by mass, 8%-25% of Pd, 0.5%-4.5% of Sc, 5%-15% of CNT and the balance Zn. The catalyst is prepared by coprecipitation reaction and is high in activity, selectivity and operation stability, stable, convenient to prepare and good in repeatability, yield of products H2 is 1.73 times of that of the products H2 of a raw matrix catalyst Pd015Zn1 not subjected to promotion in the same reaction conditions, and operation cycle life of the catalyst is obvious longer than those of similar or related catalysts.
Description
Technical field
The present invention relates to a kind of catalyst, especially a kind of Catalysts and its preparation method for hydrogen production from methanol-steam reforming.
Background technology
The progress of on-board hydrogen fuel cell technology, has promoted the development of portable hydrogen producing technology.Methyl alcohol has reaction temperature as the raw material of on-board hydrogen generation system and pressure is low, H/C than high, without NO
x, SO
xemission, and can be applicable to the advantages such as existing power fuel distributing system, thereby receive much concern.The existing many-sided report of research that methanol steam reforming (Methanol steam reforming, is abbreviated as MSR) is fuel cell hydrogen-feeding.The demonstration of reporting for work of existing document, compares with noble metal-based catalysts, and Cu-catalyst has higher activity, generates H MSR
2/ CO
2compared with high selectivity (A.P.Tsai, et al., Appl.Catal.A, 2001,214:237 – 241; Y.Liu, et al.Appl.Catal.A, 2002,223:137 – 145; X.R.Zhang, et al., Fuel Process.Technol., 2003,83:183 – 192), but its processing ease sintering deactivation (D.L.Trimm, et al., Catal.Rev.2001,43:31 – 45.) at 300 ° of C temperature.The Pd/ZnO(N.Iwasa researching and developing subsequently, et al., Appl.Catal.A, 1995,125:145 – 157; Y.H.Chin, et al., Fuel Process.Technol., 2003,83:193 – 201; A.Karim, et al., J.Catal., 2006,243:420 – 427) and Pd/Ga
2o
3(H.Lorenz, et al., Appl.Catal.A, 2009,358:203-210) catalyst, because it generates H to MSR
2/ CO
2demonstrate higher selective and heat endurance and receive much concern; Above-mentioned document is reported for work: at Pd/ZnO and Pd/Ga
2o
3in catalyst, the generation of Pd-Zn or Pd-Ga alloy plays an important role to the raising of the activity and selectivity of catalyst.But from practical standpoint, consider Pd/ZnO or Pd/Ga
2o
3the activity of catalyst, especially its operational stability (service life) is still in urgent need to be improved.
Summary of the invention
Object of the present invention aims to provide a kind of Catalysts and its preparation method for hydrogen production from methanol-steam reforming.Prepared catalyst has high activity and high selectivity, and stable, operation lifetime is long, can effectively improve the characteristics such as the one-pass yield of hydrogen production from methanol-steam reforming and life-span in operation cycle.
The described catalyst for hydrogen production from methanol-steam reforming is the two co-precipitation type palladium zinc-base catalyst that promote of CNT and scandium, and catalyst comprises major constituent and promoter, and described major constituent is Pd and ZnO, and promoter is CNT (CNT) and scandium oxide (Sc
2o
3), the chemical formulation of catalyst is: Pd
izn
jsc
k-x%CNT, in formula, subscript i, j, k are the molar ratio coefficient of Pd, Zn, Sc in catalyst, x% is that CNT is Pd at metering-type
izn
jsc
kshared mass percent in the catalyst of-x%CNT.The mass percent of the described catalyst each component for hydrogen production from methanol-steam reforming is respectively Pd:8%～25%, Sc:0.5%～4.5%, and CNT:5%～15%, surplus is Zn; Be preferably Pd:15%～18%, Sc:2.5%～4.0%, CNT:8%～12%, surplus is Zn.
The described catalyst for hydrogen production from methanol-steam reforming, Pd derives from its slaine, as PdCl
2deng.
The described catalyst for hydrogen production from methanol-steam reforming, ZnO derives from its slaine, as Zn (NO
3)
2deng.
The described catalyst for hydrogen production from methanol-steam reforming, Sc
2o
3derive from its slaine, as Sc (NO
3)
3deng.
Described CNT is multi-walled carbon nano-tubes, outer tube diameter 10 ~ 60nm, interior caliber 3～8nm, total carbon content >=99.5wt%, graphitic carbon content >=90wt%.
The preparation method of the described catalyst for hydrogen production from methanol-steam reforming is as follows:
1) by the composition and ratio for the catalyst of hydrogen production from methanol-steam reforming by the PdCl of metering
2, Zn (NO
3)
26H
2o and Sc (NO
3)
36H
2o adds water after mixing and makes solution A, and in solution A, 3 kinds of metal cation total yield concentration are 1.5～2.5N/L;
2) by the Na of metering
2cO
3the water-soluble solution B of making, Na in solution B
+the equivalent concentration of ion is identical with 3 kinds of metal cation total yield concentration in solution A;
3) at 60～80 ℃, solution A is injected to the container put in advance part amount solution B, and the addition by regulation and control solution B with the pH value that maintains coprecipitation reaction system 9～10, after reaction finishes, by feed liquid filtration, obtain sediment;
4) by step 3) gained sediment through washing to Na in leacheate
+ion concentration is rear filtration below 0.1ppm, and filter cake is mixed to making beating with amount of calculation CNT, and by centrifugal filtration, filter cake is dried rear roasting, obtains the catalyst P d for hydrogen production from methanol-steam reforming
izn
jsc
k-x%CNT(oxidation state).
In step 4), described bake out temperature can be 105～120 ℃, and drying time can be 8～12h; Described sintering temperature can be 350～400 ℃, and roasting time can be 2 ~ 4h.
Catalyst for hydrogen production from methanol-steam reforming carries out in pressurization static bed continuous flow reactor-GC combined system the catalytically active assessment of the steam reforming reaction of methyl alcohol.Each evaluation test catalyst amount 0.1～0.2g(granularity 20～40 orders).The steam reforming reaction of methyl alcohol is at 0.5MPa, and 250 ℃ or 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=7.5/7.5/85 or 30/30/40 (mol ratio), carries out under the reaction condition of air speed GHSV=108000mL/ (hg) or 180000mL/ (hg).Before reaction, oxidized catalyst is carried out original position prereduction activation in normal pressure, pure hydrogen (99.999%) reduction air-flow (flow velocity is 30mL/min), and the highest reduction temperature is 250 ℃, and whole process is lasted 4～6h; After to be adjusted to reaction temperature required, switch to import reactor feed gas and carry out methanol steam reforming reaction.The reaction end gas of discharging from reactor outlet through condenser 5～10 ℃ of condensations, divide the product liquid of leaving away, after gaseous product direct sending gas chromatograph six-way valve is sampled, thermal conductivity detector (TCD) (TCD) outfit by Shimadzu GC-2014 type gas chromatograph (Japanese Shimadzu) are done on-line analysis with carbon molecular sieve post (TDX-01, column length 2.0m).Experimental result shows, CO
2with CO be only two kinds of carbonaceous products under this reaction condition.Thereby, CO
2with selectively can being measured by inner normalization method of CO; Methanol conversion and H
2space-time yield can pass through CO
2calculated with the productive rate of CO.
The activity of prepared methanol steam reforming catalyst, selective and operational stability is high and stable, product H
2one-pass yield and the life-span in operation cycle all apparently higher than existing similar or associated catalysts, and simple for production, reproducible.
Accompanying drawing explanation
Fig. 1 is Pd
0.15zn
1sc
0.067the reactivity of-10%CNT catalyst methanol steam reforming and operational stability figure.In Fig. 1, abscissa is reaction time (h), the conversion ratio that ordinate is methyl alcohol (%), or CO
2selective (%), or H
2space-time yield (mol/ (hg)); Mark is methanol conversion, and ★ is CO
2selectively, zero is H
2space-time yield; Reaction condition is: 0.5MPa, 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=30/30/40 (mol ratio), air speed GHSV=180000mL/ (hg).
Fig. 2 is the Pd of non-promotion
0.15zn
1the reactivity of substrate catalyst catalysis methanol steam reforming and operational stability figure.In Fig. 2, abscissa is reaction time (h), the conversion ratio that ordinate is methyl alcohol (%), or CO
2selective (%), or H
2space-time yield (mol/ (hg)); Mark is methanol conversion, and ★ is CO
2selectively, zero is H
2space-time yield.
The specific embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
By 0.890g(0.00502mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 0.746g(0.00220mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.298g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.15zn
1sc
0.066-10%CNT.
Catalyst activity evaluation is carried out in pressurization static bed continuous flow reactor-GC combined system.Catalyst amount 0.12g(granularity 20～40, about 0.1mL).Before reaction, oxidized catalyst is carried out original position prereduction in normal pressure, pure hydrogen (99.999%) reduction air-flow (flow velocity is 30mL/min), and the highest reduction temperature is 250 ℃, and whole process is lasted 5h; After to be adjusted to reaction temperature required, switch to import reactor feed gas and carry out methanol steam reforming reaction.The reaction end gas of discharging from reactor outlet through condenser 10 ℃ of condensations, divide the product liquid of leaving away, after gaseous product direct sending gas chromatograph six-way valve is sampled, thermal conductivity detector (TCD) (TCD) outfit by Shimadzu GC-2014 type gas chromatograph (Japanese Shimadzu) are done on-line analysis with carbon molecular sieve post (TDX-01, column length 2.0m).CO
2with selectively being measured by inner normalization method of CO; Methanol conversion and H
2space-time yield via CO
2calculation of yield with CO.
Evaluation result is in Table 1, and result shows, at 0.5MPa, 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=30/30/40 (mol ratio), under the reaction condition of air speed GHSV=180000mL/ (hg), CO
2with CO be only two kinds of carbonaceous products, conversion ratio and the corresponding H of reaction methyl alcohol during 75h
2space-time yield remain on respectively 21.4% and the level of 1.56mol/ (hg); As can see from Figure 1, last 150h methanol steam reforming reaction operational stability good.
As a comparison, the former substrate catalyst Pd of non-promotion
0.15zn
1under identical reaction condition, conversion ratio and the corresponding H of methyl alcohol during reaction 75h
2space-time yield be only respectively 12.7% and 0.90mol/ (hg) (in Table 1), this H
2productive rate only reaches Pd
0.15zn
1sc
0.06658% of the analog value of-10%CNT catalyst (1.56mol/ (hg)); And the Pd that carries out non-promotion along with reaction
0.15zn
1the obvious (see figure 2) of catalyst operational stability downward trend.
The catalytic performance test result of table 1 embodiment 1 catalyst to hydrogen production from methanol-steam reforming
Embodiment 2
By 0.890g(0.00502mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 1.154(0.00340mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.310g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.15zn
1sc
0.1-10%CNT.
Catalyst activity evaluation experimental is with embodiment 1.Evaluation result is in Table 2, and at 0.5MPa, 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=30/30/40 (mol ratio), under the reaction condition of air speed GHSV=180000mL/ (hg), conversion ratio and the corresponding H of methyl alcohol during reaction 75h
2space-time yield only reach respectively 12.9% and 0.91mol/ (hg).
Embodiment 3
By 0.890g(0.00502mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 0.577(0.00170mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.296g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.15zn
1sc
0.05-10%CNT.
Catalyst activity evaluation experimental is with embodiment 1.Evaluation result is in Table 2, and at 0.5MPa, 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=30/30/40 (mol ratio), under the reaction condition of air speed GHSV=180000mL/ (hg), conversion ratio and the corresponding H of methyl alcohol during reaction 75h
2space-time yield only reach respectively 19.0% and 1.31mol/ (hg).
Embodiment 4
By 0.593g(0.00333mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 0.746(0.00220mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.280g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.1zn
1sc
0.066-10%CNT.
Catalyst activity evaluation experimental is with embodiment 1.Evaluation result is in Table 2, and at 0.5MPa, 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=30/30/40 (mol ratio), under the reaction condition of air speed GHSV=180000mL/ (hg), conversion ratio and the corresponding H of methyl alcohol during reaction 75h
2space-time yield only reach respectively 17.7% and 1.26mol/ (hg).
Embodiment 5
By 1.187g(0.00671mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 0.746(0.00220mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.317g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.2zn
1sc
0.066-10%CNT.
Catalyst activity evaluation experimental is with embodiment 1.Evaluation result is in Table 2, and at 0.5MPa, 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=30/30/40 (mol ratio), under the reaction condition of air speed GHSV=180000mL/ (hg), conversion ratio and the corresponding H of methyl alcohol during reaction 75h
2space-time yield only reach respectively 19.1% and 1.28mol/ (hg).
Embodiment 6
By 0.890g(0.00502mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 0.115(0.00034mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.144g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.15zn
1sc
0.01-5%CNT.
Catalyst activity evaluation experimental is with embodiment 1.Evaluation result is in Table 2, and at 0.5MPa, 250 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=7.5/7.5/85 (mol ratio), under the reaction condition of air speed GHSV=108000mL/ (hg), conversion ratio and the corresponding H of methyl alcohol during reaction 12h
2space-time yield reach respectively 61.6% and 0.66mol/ (hg).
Embodiment 7
By 0.890g(0.00502mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 0.115(0.00034mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.304g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.15zn
1sc
0.01-10%CNT.
Catalyst activity evaluation experimental is with embodiment 1.Evaluation result is in Table 2, and at 0.5MPa, 250 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=7.5/7.5/85 (mol ratio), under the reaction condition of air speed GHSV=108000mL/ (hg), conversion ratio and the corresponding H of methyl alcohol during reaction 12h
2space-time yield reach respectively 66.8% and 0.72mol/ (hg).
Embodiment 8
By 0.890g(0.00502mol) PdCl
2, 9.970g(0.0335mol) Zn (NO
3)
26H
2o and 0.115(0.00034mol) Sc (NO
3)
36H
2o(purity is all AR level) be mixed together, add 50mL deionized water to be mixed with solution A; Separately by 13.250g(0.125mol) AR level anhydrous Na
2cO
3be dissolved in 125mL deionized water and make solution B.At 60 ℃ of temperature, solution A is injected to the 500mL beaker (charge velocity is about 18mL/min) of putting in advance part amount solution B, at 60 ℃ of constant temperature and constantly carry out coprecipitation reaction under stirring condition, the addition by regulator solution B makes the pH value of precipitated liquid remain 9～10 scopes.Reinforced finishing, continues to stir 30min, after feed liquid is filtered, gained sediment repeatedly washs through deionized water, until Na in leacheate
+ion concentration is rear filtration below 0.1ppm, filter cake at room temperature mixed to making beating 4h with 0.483g CNT, by centrifugal filtration, gained solid content is dried 10h in 110 ℃ of temperature, 360 ℃ of roasting 2h, obtain the methanol steam reforming catalyst (oxidation state) prepared of wish, its chemical expression formula is Pd
0.15zn
1sc
0.01-15%CNT.
Catalyst activity evaluation experimental is with embodiment 1.Evaluation result is in Table 2, and at 0.5MPa, 250 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=7.5/7.5/85 (mol ratio), under the reaction condition of air speed GHSV=108000mL/ (hg), conversion ratio and the corresponding H of methyl alcohol during reaction 12h
2space-time yield reach respectively 59.0% and 0.63mol/ (hg).
Embodiment 9～16
The preparation method of catalyst and assessment process are with embodiment 1; The content of catalyst components and to methanol steam reforming H processed
2catalytic performance test the results are shown in Table 3.
Table 2. catalyst is to methanol steam reforming H processed
2catalytic performance test result
Table 3. catalyst is to methanol steam reforming H processed
2catalytic performance test result
Note: 1) stoichiometric equation of palladium bichloride used, zinc nitrate and scandium nitrate is respectively: PdCl
2, Zn (NO
3)
26H
2o and Sc (NO
3)
36H
2o, purity is AR level; CNT is prepared voluntarily, and its structure is " fish bone well " multi-walled carbon nano-tubes, outer tube diameter 10 ~ 60nm, interior caliber 3～8nm, total carbon content>=99.5wt% graphitic carbon content>=90wt%.
2) reaction condition is: (1) 0.5MPa, 275 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=30/30/40 (mol ratio), air speed GHSV=180000mL/ (hg); Or (2) 0.5MPa, 250 ℃, unstripped gas consists of CH
3oH/H
2o/N
2=7.5/7.5/85 (mol ratio), air speed GHSV=108000mL/ (hg).
Claims (8)
1. the catalyst for hydrogen production from methanol-steam reforming, it is characterized in that for CNT and the two co-precipitation type palladium zinc-base catalyst that promote of scandium, catalyst comprises major constituent and promoter, described major constituent is Pd and ZnO, promoter is CNT (CNT) and scandium oxide, and the chemical formulation of catalyst is: Pd
izn
jsc
k-x%CNT, in formula, subscript i, j, k are the molar ratio coefficient of Pd, Zn, Sc in catalyst, x% is that CNT is Pd at metering-type
izn
jsc
kshared mass percent in the catalyst of-x%CNT;
The mass percent of the described catalyst each component for hydrogen production from methanol-steam reforming is respectively Pd:8%～25%, Sc:0.5%～4.5%, and CNT:5%～15%, surplus is Zn;
Described CNT is multi-walled carbon nano-tubes, outer tube diameter 10～60nm, interior caliber 3～8nm, total carbon content >=99.5wt%, graphitic carbon content >=90wt%.
2. a kind of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, the mass percent that it is characterized in that the described catalyst each component for hydrogen production from methanol-steam reforming is respectively Pd:15%～18%, Sc:2.5%～4.0%, CNT:8%～12%, surplus is Zn.
3. a kind of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, is characterized in that the described catalyst for hydrogen production from methanol-steam reforming, and Pd derives from its slaine, and described slaine can adopt PdCl
2.
4. a kind of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, is characterized in that the described catalyst for hydrogen production from methanol-steam reforming, and ZnO derives from its slaine, and described slaine can adopt Zn (NO
3)
2.
5. a kind of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, is characterized in that the described catalyst for hydrogen production from methanol-steam reforming, Sc
2o
3derive from its slaine, described slaine can adopt Sc (NO
3)
3.
6. as the preparation method of a kind of catalyst for hydrogen production from methanol-steam reforming as described in arbitrary in claim 1～5, it is characterized in that comprising the following steps:
1) by the composition and ratio for the catalyst of hydrogen production from methanol-steam reforming by the PdCl of metering
2, Zn (NO
3)
26H
2o and Sc (NO
3)
36H
2o adds water after mixing and makes solution A, and in solution A, 3 kinds of metal cation total yield concentration are 1.5～2.5N/L;
2) by the Na of metering
2cO
3the water-soluble solution B of making, Na in solution B
+the equivalent concentration of ion is identical with 3 kinds of metal cation total yield concentration in solution A;
3) at 60～80 ℃, solution A is injected to the container put in advance part amount solution B, and the addition by regulation and control solution B with the pH value that maintains coprecipitation reaction system 9～10, after reaction finishes, by feed liquid filtration, obtain sediment;
4) by step 3) gained sediment through washing to Na in leacheate
+ion concentration is rear filtration below 0.1ppm, and filter cake is mixed to making beating with amount of calculation CNT, and by centrifugal filtration, filter cake is dried rear roasting, obtains the catalyst P d for hydrogen production from methanol-steam reforming
izn
jsc
k-x%CNT(oxidation state).
7. the preparation method of a kind of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 6, is characterized in that in step 4), and described bake out temperature is 105～120 ℃, and drying time is 8～12h.
8. the preparation method of a kind of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 6, is characterized in that in step 4), and described sintering temperature is 350～400 ℃, and roasting time is 2～4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210403330.6A CN102872867B (en) | 2012-10-19 | 2012-10-19 | Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210403330.6A CN102872867B (en) | 2012-10-19 | 2012-10-19 | Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102872867A CN102872867A (en) | 2013-01-16 |
| CN102872867B true CN102872867B (en) | 2014-05-07 |
Family
ID=47474512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210403330.6A Expired - Fee Related CN102872867B (en) | 2012-10-19 | 2012-10-19 | Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102872867B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108525655B (en) * | 2018-05-03 | 2020-07-24 | 扬州工业职业技术学院 | Preparation method and application of novel composite catalyst for oxidizing hydroxyl into carbonyl |
| CN111153384A (en) * | 2019-12-31 | 2020-05-15 | 四川天采科技有限责任公司 | Direct methanol cracking preparation of H2Catalytic and permeable integrated membrane reactor and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597104A (en) * | 2004-08-20 | 2005-03-23 | 上海舜华新能源系统有限公司 | Integral catalyst for preparation hydrogen by methyl alcohot reformation and its preparation method |
| CN101444731A (en) * | 2008-12-31 | 2009-06-03 | 厦门大学 | Catalyst used for preparing methanol by hydrogenation of carbon dioxide and a preparation method thereof |
| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| CN101500706A (en) * | 2006-06-28 | 2009-08-05 | 新日本石油株式会社 | Catalyst for steam reformation, hydrogen production apparatus, and fuel cell system |
| CN101733089A (en) * | 2008-11-25 | 2010-06-16 | 中国科学院物理研究所 | Catalyst for preparing hydrogen gas, method for preparing same and application thereof |
| KR20120024841A (en) * | 2009-05-26 | 2012-03-14 | 바스프 코포레이션 | Methanol steam reforming catalysts |
-
2012
- 2012-10-19 CN CN201210403330.6A patent/CN102872867B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597104A (en) * | 2004-08-20 | 2005-03-23 | 上海舜华新能源系统有限公司 | Integral catalyst for preparation hydrogen by methyl alcohot reformation and its preparation method |
| CN101500706A (en) * | 2006-06-28 | 2009-08-05 | 新日本石油株式会社 | Catalyst for steam reformation, hydrogen production apparatus, and fuel cell system |
| CN101733089A (en) * | 2008-11-25 | 2010-06-16 | 中国科学院物理研究所 | Catalyst for preparing hydrogen gas, method for preparing same and application thereof |
| CN101444731A (en) * | 2008-12-31 | 2009-06-03 | 厦门大学 | Catalyst used for preparing methanol by hydrogenation of carbon dioxide and a preparation method thereof |
| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| KR20120024841A (en) * | 2009-05-26 | 2012-03-14 | 바스프 코포레이션 | Methanol steam reforming catalysts |
Non-Patent Citations (4)
| Title |
|---|
| Pd/ZnO催化剂上甲醇水蒸气重整制氢;王艳华等;《化工学报》;20060430;第57卷(第4期);第775-779页 * |
| Pd/ZnO催化剂的还原及其催化甲醇水蒸气重整制氢;王艳华等;《催化学报》;20070331;第28卷(第3期);摘要，第235页左栏第3段 * |
| 王艳华等.Pd/ZnO催化剂上甲醇水蒸气重整制氢.《化工学报》.2006,第57卷(第4期), |
| 王艳华等.Pd/ZnO催化剂的还原及其催化甲醇水蒸气重整制氢.《催化学报》.2007,第28卷(第3期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102872867A (en) | 2013-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103896768B (en) | A kind of method preparing methyl acetate | |
| CN106390978B (en) | A kind of high temperature resistant synthesizing methanol by hydrogenating carbon dioxide catalyst and its preparation and application | |
| CN101703933B (en) | Bimetal methanation catalyst and preparation method thereof | |
| CN102847544B (en) | Catalytic agent for preparing ethanol by using acetic acid hydrogenation and preparation method thereof | |
| CN103896769B (en) | A kind of method of preparing methyl acetate by carbonylating dimethyl ether | |
| Jiang et al. | Catalytic performance of Pd–Ni bimetallic catalyst for glycerol hydrogenolysis | |
| CN103084186B (en) | For directly being prepared Catalysts and its preparation method and the purposes of ethanol by acetic acid | |
| CN102847535A (en) | Catalyst for preparation of ethanol through acetic acid hydrogenation and preparation method thereof | |
| CN104162424A (en) | Preparation method of cerium oxide-supported palladium catalyst and application of palladium catalyst in CO catalytic oxidation | |
| CN110102294B (en) | Composite oxide loaded Pd-based catalyst, and preparation method and application thereof | |
| CN102145876B (en) | Method for producing hydrogen by reforming methanol steam | |
| CN105859555B (en) | A kind of method that dehydrogenation prepares methyl formate under methanol normal pressure | |
| CN108499566A (en) | A kind of preparation method and application of CuNi bases catalyst | |
| CN101972656A (en) | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof | |
| CN107159217A (en) | A kind of Cu ZnO/SiO2Aeroge bimetallic catalyst and its production and use | |
| CN102872867B (en) | Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst | |
| CN105435779B (en) | Carbon monoxide vapor- phase synthesis oxalate catalyst | |
| CN105080564B (en) | Catalyst and its application method for carbon dioxide conversion carbon monoxide | |
| CN101284774A (en) | Process for preparing glyceric acid by one-step of direct catalytic oxidation with oxygen | |
| CN106518619A (en) | Method for preparing ethyl alcohol by hydrogenation of acetate | |
| CN104193606A (en) | Technique for preparing acetone from synthetic gas | |
| CN103170338B (en) | A kind of catalyst for being used for 1,2 propane diols and preparation method thereof | |
| CN105749913B (en) | The catalyst and acetate preparation of ethanol through hydrogenation method of acetate preparation of ethanol through hydrogenation | |
| CN102407126B (en) | Catalyst used for preparing synthetic natural gas by using coal derived synthesis gas and preparation method thereof | |
| CN102941098A (en) | Catalyst for methane synthesis through carbon dioxide hydrogenation and preparation method thereof |
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 |
Granted publication date: 20140507 Termination date: 20191019 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |