CN109603834A - A kind of catalyst and preparation method thereof for hydrogen production from methanol-steam reforming - Google Patents
A kind of catalyst and preparation method thereof for hydrogen production from methanol-steam reforming Download PDFInfo
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- CN109603834A CN109603834A CN201811544210.1A CN201811544210A CN109603834A CN 109603834 A CN109603834 A CN 109603834A CN 201811544210 A CN201811544210 A CN 201811544210A CN 109603834 A CN109603834 A CN 109603834A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Abstract
The present invention relates to a kind of catalyst for hydrogen production from methanol-steam reforming, component includes Cu, La2O3And ZrO2；It is in terms of 100% by the metallic atom total mole number in catalyst, the molar percentage that the molar percentage that the molar percentage of La is 1~5%, Cu is 5~40%, Zr is 55~94%；The preparation method of the catalyst is the following steps are included: first by the mixed solution of copper nitrate, lanthanum nitrate and zirconium oxychloride and sodium carbonate liquor parallel-flow precipitation, form colloidal sol, further aging, solvent evaporated forms gel, drying and roasting, it is handled again by dust technology, roasting obtains the catalyst for hydrogen production from methanol-steam reforming again；The present invention compared with the existing technology, using acid handles Cu/La2O3/ZrO2Catalyst can handle the copper component with the weak effect of carrier, to make copper zirconium interface sufficiently expose, therefore catalyst activity and stability dramatically increase.
Description
[technical field]
The invention belongs to chemical technology field, specifically a kind of catalyst for hydrogen production from methanol-steam reforming and
Preparation method.
[background technique]
Methanol cluster (MSR) hydrogen production reaction replacing as fuel cell, especially Proton Exchange Membrane Fuel Cells
For hydrogen source, have many advantages, such as that noble metal catalyst is commonly used in clean, efficient, convenient transportation, the valence of the expensive catalyst
Lattice limit its popularity.Copper catalyst due to the advantages that cheap, high catalytic activity gain great popularity in recent years but due to
The catalyst such as CuZnAl and CuCr are easy inactivation in hydrogen production from methanol-steam reforming reaction process, and have a certain amount of CO pair
The disadvantages of generation of product, limits its hydrogen source for directly applying to PEMFC.Therefore, the stabilization of copper-based catalysts how is improved
Property, the generation of CO is reduced, at present one of the project to improve the copper catalyst most important thing.
It can be found by literature survey, copper component is easy aggregation in the reduction and reaction process of catalyst agent
The main reason for growing up, becoming the activity reduction of catalyst.Meanwhile more and more evidences support Cu+Species are reacted in catalysis
In even more important be passed through the gas (CO of a small amount of oxidisability in the reaction system2Or O2), Cu catalyst can be significantly improved
Activity and stability.Catalytic activity result of study is further showed that by using model catalyst, the activity of catalyst is same
There is corresponding relationships between the oxygen species on copper surface.Therefore, the oxygen species on stabilized copper surface become the core of this field research
Content.
Study copper-based catalysts different type carrier the result shows that, ZrO2Component effectively can form table by Dissociative water
Face hydroxyl can directly react with ADSORPTION STATE methanol and generate CO2And hydrogen, so as to avoid disappearing for copper surface oxygen species
Consume and stabilize the oxygen species of catalyst surface.In addition, if rare-earth additive is introduced in the catalyst, not only to catalyst structure
Play the role of stablizing and optimize, prevents copper from roasting, agglomeration in reduction and reaction process, and the catalyst promoted
The formation at the activated centre interface Tong Gao increases Cu+The content of species further increases the activity of catalyst.But in catalyst
In preparation process, always there are the copper species weaker with carrier function, and the effect is with the increase of copper content in catalyst
It becomes apparent, these copper species not only cover the copper zirconium interface of catalyst, but also in catalyst heat treatment process, are easy poly-
Collection is grown up, so as to cause the activity decline of catalyst.
If Cu/La can be prepared using coprecipitation2O3/ZrO2Catalyst, then using the copper of acid processing and the weak effect of carrier
Component improves the activity and stability of catalyst so that copper zirconium interface be made sufficiently to expose；To copper catalyst activated centre characterization and
On the basis of understanding, it is carried out further to be modified to have very important significance to improve its activity and stability.
[summary of the invention]
A kind of urging for hydrogen production from methanol-steam reforming is provided present invention aim to solve above-mentioned deficiency
Agent, the catalyst activity and stability dramatically increase, and preparation method is simple, and preparation expense significantly reduces, while into one
Step reduces waste liquor contamination.
Design a kind of catalyst for hydrogen production from methanol-steam reforming to achieve the above object, component include Cu,
La2O3And ZrO2；It is in terms of 100% by the metallic atom total mole number in catalyst, the molar percentage of La is 1~5%, Cu's
The molar percentage that molar percentage is 5~40%, Zr is 55~94%.
Further, it is mole of 10~30%, Zr that the molar percentage of the La, which is the molar percentage of 2~4%, Cu,
Percentage is 66~88%.
The present invention also provides a kind of preparation methods of above-mentioned catalyst, comprising the following steps: first by copper nitrate, nitric acid
The mixed solution and sodium carbonate liquor parallel-flow precipitation of lanthanum and zirconium oxychloride form colloidal sol, and further aging, solvent evaporated forms solidifying
Glue, drying and roasting, then handled by dust technology, roasting is made again.
Further, in the preparation method, the copper nitrate, lanthanum nitrate, zirconium oxychloride inventory be converted to metal original
Son is in terms of 100% by metallic atom total mole number, the molar percentage that the molar percentage of La is 1~5%, Cu is 5~
The molar percentage of 40%, Zr are 55~94%.
Further, in the preparation method, during nitric acid treatment, the molar ratio of the nitric acid and copper is 1~1.2:1,
Concentration of nitric acid is 0.25~1.5mol/L.
The preparation method of the catalyst, the specific steps are as follows:
1) by a certain proportion of Cu (NO3)2.3H2O、La(NO3)3.6H2O and ZrOCl2.8H2O formation mixing soluble in water is molten
Liquid, by the sodium carbonate liquor of mixed solution and 0.9-1.1mol/L, cocurrent is added drop-wise in the beaker equipped with water dropwise, controls cocurrent
Each droplets amount be 0.05~0.07ml, by adjust 1mol/L sodium carbonate liquor drop rate, using pH meter will
Suspension pH value control in 9.5~10 ranges, be added dropwise during control speed of agitator be 200-300r/min, temperature 60 C,
Solution completion of dropwise addition to be mixed continues stirring ageing 1h after forming colloidal sol, then filters, is washed with distilled water filter cake until filtrate
It can't detect Cl with the silver nitrate solution of 0.1mol/L-1Until, then by filter cake through 110~120 DEG C of 10~12h of baking, then in 400
~450 DEG C of roasting 4h；
2) sample obtained by step 1) is worn into and is poured into the nitric acid of 0.5~1.5mol/L less than after 100 mesh powder, and constantly
30min is stirred, then speed of agitator 200-300r/min is filtered, wash three times, then through 110~120 DEG C of 4~6h of baking, then
In 400~450 DEG C of roasting 4h to get the catalyst for hydrogen production from methanol-steam reforming.
The present invention compared with the existing technology, has the advantages that
(1) catalyst of the invention is using acid processing Cu/La2O3/ZrO2Catalyst can handle and the weak effect of carrier
Copper component, so that copper zirconium interface be made sufficiently to expose, therefore catalyst activity and stability are dramatically increased；
(2) system for catalyst can be recycled in catalyst preparation process of the present invention by the copper component that nitric acid reaction falls
It is standby, therefore the preparation expense of catalyst significantly reduces, while further reduced waste liquor contamination, and preparation method is simple, obtains
Catalyst activity it is high, be easy to carry out industrial amplification；
(3) present invention handles the copper component with the weak effect of carrier using acid, to make copper zirconium interface sufficiently expose, with ZrO2
The same component pretended forms Cu abundant in reduction process+Species, and reaction species are in the extraction effect at copper zirconium interface
Also enhancing, therefore catalyst maintains the activity and stability of higher catalysis, catalyst shows initial activity at 190 DEG C,
In 230 DEG C of catalyst methanol conversions more than 80%, and the selectivity of CO is below 1%；
(4) catalyst prepared by the present invention for hydrogen production from methanol-steam reforming is through H2After/He gas activation processing, table
Reveal high catalytic activity and stability, the content of by-product CO is lower than 0.5%；
(5) present invention is to Cu/La2O3/ZrO2On the basis of catalyst active center's characterization and understanding, using co-precipitation
Method prepares Cu/La2O3/ZrO2Catalyst, then using the copper component of acid processing and the weak effect of carrier, so that copper zirconium interface be made to fill
Divide exposure, improves the activity and stability of catalyst, be worthy of popularization.
[specific embodiment]
The present invention provides a kind of catalyst for hydrogen production from methanol-steam reforming, component includes Cu, La2O3With
ZrO2；By the metallic atom total mole number in catalyst it is in terms of 100% that the molar percentage of La is 1~5%, preferably 2~
The molar percentage of 4%, Cu are 5~40%, and preferably the molar percentage of 10~30%, Zr is 55~94%, preferably 66
~88%.The catalyst the preparation method comprises the following steps: first that the mixed solution of copper nitrate, lanthanum nitrate and zirconium oxychloride and sodium carbonate is molten
Liquid parallel-flow precipitation forms colloidal sol, further aging, and solvent evaporated forms gel, drying and roasting, then is handled by dust technology, then
Secondary roasting is made.Wherein, copper nitrate, lanthanum nitrate, zirconium oxychloride inventory be converted to metallic atom, with metallic atom total moles
Number is 100% meter, and the molar percentage that the molar percentage that the molar percentage of La is 1~5%, Cu is 5~40%, Zr is 55
~94%；In sour treatment process, the molar ratio of nitric acid and copper is 1~1.2:1, and concentration of nitric acid is 0.25~1.5mol/L.
The present invention is made combined with specific embodiments below further explained below:
Embodiment 1
A kind of above-mentioned catalyst for hydrogen production from methanol-steam reforming, takes sour treatment gel method, i.e., first by nitric acid
Copper, the mixed solution of lanthanum nitrate and zirconium oxychloride and sodium carbonate liquor parallel-flow precipitation, form colloidal sol, and further aging is evaporated molten
Dosage form is at gel, drying and roasting, then is handled by dust technology, and roasting is made again.
The molar percentage of each metallic atom contained in the catalyst calculates, specific as follows:
La 1%
Cu 5%
Zr 94%.
The preparation method specifically comprises the following steps:
1) by 1gCu (NO3)2.3H2O、0.36gLa(NO3)3.6H2O and 26.2g ZrOCl2.8H2O is dissolved in the water of 160mL
Mixed solution is formed, cocurrent is added drop-wise to the water equipped with 20mL dropwise by the sodium carbonate liquor of mixed solution and 250mL 1mol/L
In beaker, and the amount for controlling each droplets of cocurrent is 0.05-0.07ml, the dropwise addition of the sodium carbonate liquor by adjusting 1mol/L
Rate is controlled suspension pH value in 9.5~10 ranges using pH meter, and control speed of agitator is 200-300r/ during being added dropwise
Min, temperature is 60 DEG C, after solution completion of dropwise addition to be mixed forms colloidal sol, continues stirring ageing 1h, then filters, use distilled water
Washing filter cake is until filtrate can't detect Cl with the silver nitrate solution of 0.1mol/L-1Until, then by filter cake through 120 DEG C of baking 12h, so
Afterwards in 450 DEG C of roasting 4h；
2) the resulting sample of 8g step 1) is worn into and is poured into the nitric acid of 20mL0.25mol/L less than after 100 mesh powder, and
Be stirred continuously 30min, then speed of agitator 200-300r/min is filtered, wash three times, then through 120 DEG C of baking 5h, then in
450 DEG C of roasting 4h are to get the catalyst A for hydrogen production from methanol-steam reforming.
Embodiment 2
A kind of above-mentioned catalyst for hydrogen production from methanol-steam reforming, takes sour treatment gel method, i.e., first by nitric acid
Copper, the mixed solution of lanthanum nitrate and zirconium oxychloride and sodium carbonate liquor parallel-flow precipitation, form colloidal sol, and further aging is evaporated molten
Dosage form is at gel, drying and roasting, then is handled by dust technology, and roasting is made again.
The molar percentage of each metallic atom contained in the catalyst calculates, specific as follows:
La 2%
Cu 20%
Zr 78%.
The preparation method specifically comprises the following steps:
1) by 4.2gCu (NO3)2.3H2O、0.8gLa(NO3)3.6H2O and 22.9g ZrOCl2.8H2O is dissolved in the water of 160mL
Middle formation mixed solution, by the sodium carbonate liquor of mixed solution and 250mL 1mol/L, cocurrent is added drop-wise to the water equipped with 20mL dropwise
Beaker in, and control cocurrent each droplets amount be 0.05-0.07ml, pass through adjust 1mol/L sodium carbonate liquor drop
Rate of acceleration is controlled suspension pH value in 9.5~10 ranges using pH meter, and control speed of agitator is 200- during being added dropwise
300r/min, temperature 60 C, solution completion of dropwise addition to be mixed continue stirring ageing 1h after forming colloidal sol, then filter, with distillation
Water washing filter cake is until filtrate can't detect Cl with the silver nitrate solution of 0.1mol/L-1Until, then by filter cake through 120 DEG C of baking 12h,
Then in 450 DEG C of roasting 4h.
2) 8g is worn into according to sample prepared by step 1) less than the nitre for pouring into 35mL 0.5mol/L after 100 mesh powder
In acid, and it being stirred continuously 30min, then speed of agitator 200-300r/min is filtered, it washs three times, then through 120 DEG C of baking 5h,
Then in 450 DEG C of roasting 4h to get the catalyst B for hydrogen production from methanol-steam reforming.
Embodiment 3
A kind of above-mentioned catalyst for hydrogen production from methanol-steam reforming, takes sour treatment gel method, i.e., first by nitric acid
Copper, the mixed solution of lanthanum nitrate and zirconium oxychloride and sodium carbonate liquor parallel-flow precipitation, form colloidal sol, and further aging is evaporated molten
Dosage form is at gel, drying and roasting, then is handled by dust technology, and roasting is made again.
The molar percentage of each metallic atom contained in the catalyst calculates, specific as follows:
La 3%
Cu 30%
Zr 67%.
The preparation method specifically comprises the following steps:
1) by 6.5gCu (NO3)2.3H2O、1.2gLa(NO3)3.6H2O and 20.1g ZrOCl2.8H2O is dissolved in the water of 160mL
Middle formation mixed solution, by the sodium carbonate liquor of mixed solution and 250mL 1mol/L, cocurrent is added drop-wise to the water equipped with 20mL dropwise
Beaker in, and control cocurrent each droplets amount be 0.05-0.07ml, pass through adjust 1mol/L sodium carbonate liquor drop
Rate of acceleration is controlled suspension pH value in 9.5~10 ranges using pH meter, and control speed of agitator is 200- during being added dropwise
300r/min, temperature 60 C, solution completion of dropwise addition to be mixed continue stirring ageing 1h after forming colloidal sol, then filter, with distillation
Water washing filter cake is until filtrate can't detect Cl with the silver nitrate solution of 0.1mol/L-1Until, then by filter cake through 120 DEG C of baking 12h,
Then in 450 DEG C of roasting 4h.
2) 8g is worn into according to sample prepared by step 1) less than the nitric acid for pouring into 27mL1mol/L after 100 mesh powder
In, and it is stirred continuously 30min, then speed of agitator 200-300r/min is filtered, wash three times, then through 120 DEG C of baking 5h, so
Afterwards in 450 DEG C of roasting 4h to get the catalyst C for hydrogen production from methanol-steam reforming.
Embodiment 4
A kind of above-mentioned catalyst for hydrogen production from methanol-steam reforming, takes sour treatment gel method, i.e., first by nitric acid
Copper, the mixed solution of lanthanum nitrate and zirconium oxychloride and sodium carbonate liquor parallel-flow precipitation, form colloidal sol, and further aging is evaporated molten
Dosage form is at gel, drying and roasting, then is handled by dust technology, and roasting is made again.
The molar percentage of each metallic atom contained in the catalyst calculates, specific as follows:
La 5%
Cu 40%
Zr 55%.
The preparation method specifically comprises the following steps:
1) by 9.0gCu (NO3)2.3H2O、2.0gLa(NO3)3.6H2O and 17.3g ZrOCl2.8H2O is dissolved in the water of 160mL
Middle formation mixed solution, by the sodium carbonate liquor of mixed solution and 250mL 1mol/L, cocurrent is added drop-wise to the water equipped with 20mL dropwise
Beaker in, and control cocurrent each droplets amount be 0.05-0.07ml, pass through adjust 1mol/L sodium carbonate liquor drop
Rate of acceleration is controlled suspension pH value in 9.5~10 ranges using pH meter, and control speed of agitator is 200- during being added dropwise
300r/min, temperature 60 C, solution completion of dropwise addition to be mixed continue stirring ageing 1h after forming colloidal sol, then filter, with distillation
Water washing filter cake is until filtrate can't detect Cl with the silver nitrate solution of 0.1mol/L-1Until, then by filter cake through 120 DEG C of baking 12h,
Then in 450 DEG C of roasting 4h.
2) 8g is worn into according to sample prepared by step 1) less than the nitre for pouring into 25mL 1.5mol/L after 100 mesh powder
In acid, and it being stirred continuously 30min, then speed of agitator 200-300r/min is filtered, it washs three times, then through 120 DEG C of baking 5h,
Then in 450 DEG C of roasting 4h to get the catalyst D for hydrogen production from methanol-steam reforming.
Embodiment 5
By the resulting catalyst A tabletting for being used for hydrogen production from methanol-steam reforming of above-described embodiment 1 and it is crushed to 20-40 mesh
It is spare.
The active testing of catalyst A for hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors,
By 0.3g be used for the catalyst A (40-60 mesh) of hydrogen production from methanol-steam reforming with etc. quality quartz sand mix after be fixed to it is anti-
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programming to 250 DEG C of reduction
Then reacting furnace temperature is dropped to setting reaction temperature by activated catalyst 8h, switch nitrogen (flow 30mL/min), and nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reaction in the stable 2h post-sampling analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and is detected by thermal conductivity detector (TCD) (TCD), controls sampling process with work station and carries out
Data processing.
Reaction condition: H2O/CH3OH=1.1/1 (molar ratio)；WHSV=4.8ml.gcat-1h-1T=230 DEG C；P=
0.1MPa
aCO2Selectivity:
Embodiment 6
By the resulting catalyst B tabletting for being used for hydrogen production from methanol-steam reforming of above-described embodiment 2 and it is crushed to 20-40 mesh
It is spare.
The active testing of catalyst B for hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors,
By 0.3g be used for the catalyst B (40-60 mesh) of hydrogen production from methanol-steam reforming with etc. quality quartz sand mix after be fixed to it is anti-
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programming to 250 DEG C of reduction
Then reacting furnace temperature is dropped to setting reaction temperature by activated catalyst 8h, switch nitrogen (flow 30mL/min), and nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reaction in the stable 2h post-sampling analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and is detected by thermal conductivity detector (TCD) (TCD), controls sampling process with work station and carries out
Data processing.
Reaction condition: H2O/CH3OH=1.1/1 (molar ratio)；WHSV=4.8ml.gcat-1h-1T=230 DEG C；P=
0.1MPa
aCO2Selectivity:
Embodiment 7
By the resulting catalyst C tabletting for being used for hydrogen production from methanol-steam reforming of above-described embodiment 3 and it is crushed to 20-40 mesh
It is spare.
The active testing of catalyst C for hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors,
By 0.3g be used for the catalyst C (40-60 mesh) of hydrogen production from methanol-steam reforming with etc. quality quartz sand mix after be fixed to it is anti-
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programming to 250 DEG C of reduction
Then reacting furnace temperature is dropped to setting reaction temperature by activated catalyst 8h, switch nitrogen (flow 30mL/min), and nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reaction in the stable 2h post-sampling analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and is detected by thermal conductivity detector (TCD) (TCD), controls sampling process with work station and carries out
Data processing.
Reaction condition: H2O/CH3OH=1.1/1 (molar ratio)；WHSV=4.8ml.gcat-1h-1T=230 DEG C；P=
0.1MPa
aCO2Selectivity:
Embodiment 8
By the resulting catalyst D tabletting for being used for hydrogen production from methanol-steam reforming of above-described embodiment 4 and it is crushed to 20-40 mesh
It is spare.
The active testing of catalyst D for hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors,
By 0.3g be used for the catalyst D (40-60 mesh) of hydrogen production from methanol-steam reforming with etc. quality quartz sand mix after be fixed to it is anti-
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programming to 250 DEG C of reduction
Then reacting furnace temperature is dropped to setting reaction temperature by activated catalyst 8h, switch nitrogen (flow 30mL/min), and nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reaction in the stable 2h post-sampling analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and is detected by thermal conductivity detector (TCD) (TCD), controls sampling process with work station and carries out
Data processing.
Reaction condition: H2O/CH3OH=1.1/1 (molar ratio)；WHSV=4.8ml.gcat-1h-1T=230 DEG C；P=
0.1MPa
aCO2Selectivity:
Embodiment 9
The resulting catalyst C for being used for indoor HCHO catalysis oxidation of embodiment 3 is used into the activity rating side with embodiment 7
Method, and keep reaction temperature constant, correspond to the conversion ratio and H of the methanol of different time2Generating rate see the table below:
Reaction condition: H2O/CH3OH=1.1/1 (molar ratio)；WHSV=4.8ml.gcat-1h-1；T=230 DEG C；P=
0.1MPa
By result above it follows that the Cu-La of nitric acid treatment preparation2O3/ZrO2Catalyst activity is high, and CO content is lower than
1%, optimum proportioning catalyst C methanol conversion can achieve 92%, CO content and only account for 0.49%, and catalyst is small by 48
When continuously run and do not find active reduction.
To sum up: Cu-La of the present invention2O3/ZrO2Catalyst is after nitric acid treatment, to hydrogen production from methanol-steam reforming
Show more excellent catalytic activity.The catalyst reaction mild condition, reactivity with higher, and by-product CO
Content is less, and the stability of catalyst is high.Separately by literature search, it did not met similar catalyst system to report, therefore the present invention has
There is novelty.
The present invention is simultaneously not limited to the embodiments described above, other any without departing from spiritual essence and principle of the invention
Changes, modifications, substitutions, combinations, simplifications made by lower, should be equivalent substitute mode, are included in protection model of the invention
Within enclosing.
Claims (6)
1. a kind of catalyst for hydrogen production from methanol-steam reforming, it is characterised in that: its component includes Cu, La2O3And ZrO2；
It is in terms of 100% by the metallic atom total mole number in catalyst, the molar percentage that the molar percentage of La is 1~5%, Cu is
The molar percentage of 5~40%, Zr are 55~94%.
2. catalyst as described in claim 1, it is characterised in that: the molar percentage of the La is 2~4%, the Cu's
Molar percentage is 10~30%, and the molar percentage of the Zr is 66~88%.
3. a kind of preparation method of catalyst as claimed in claim 1 or 2, which comprises the following steps: first will
Copper nitrate, the mixed solution of lanthanum nitrate and zirconium oxychloride and sodium carbonate liquor parallel-flow precipitation, form colloidal sol, and further aging is steamed
Dry solvent forms gel, drying and roasting, then is handled by dust technology, and roasting is made again.
4. preparation method as claimed in claim 3, it is characterised in that: the inventory of the copper nitrate, lanthanum nitrate, zirconium oxychloride
It is converted to metallic atom, is in terms of 100% by metallic atom total mole number, the molar percentage of La is moles the hundred of 1~5%, Cu
Dividing the molar percentage that ratio is 5~40%, Zr is 55~94%.
5. preparation method as claimed in claim 3, it is characterised in that: during nitric acid treatment, mole of the nitric acid and copper
Than for 1~1.2:1, the concentration of nitric acid is 0.25~1.5mol/L.
6. preparation method as claimed in claim 3, which is characterized in that specific step is as follows:
1) by a certain proportion of Cu (NO3)2.3H2O、La(NO3)3.6H2O and ZrOCl2.8H2O formation mixed solution soluble in water,
By the sodium carbonate liquor of mixed solution and 0.9-1.1mol/L, cocurrent is added drop-wise in the beaker equipped with water dropwise, controls the every of cocurrent
The amount of dropping liquid drop is 0.05~0.07ml, the drop rate of the sodium carbonate liquor by adjusting 1mol/L, will be suspended using pH meter
Liquid pH value controls in 9.5~10 ranges, and control speed of agitator is 200-300r/min, temperature 60 C, to mixed during being added dropwise
It closes after solution completion of dropwise addition forms colloidal sol and continues stirring ageing 1h, then filter, be washed with distilled water filter cake until filtrate is used
The silver nitrate solution of 0.1mol/L can't detect Cl-1Until, then by filter cake through 110~120 DEG C of 10~12h of baking, then in 400~
450 DEG C of roasting 4h；
2) sample obtained by step 1) is worn into and is poured into the nitric acid of 0.5~1.5mol/L less than after 100 mesh powder, and be stirred continuously
30min, speed of agitator 200-300r/min, is then filtered, and is washed three times, then through 110~120 DEG C of 4~6h of baking, then in
400~450 DEG C of roasting 4h are to get the catalyst for hydrogen production from methanol-steam reforming.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068681A (en) * | 2019-11-28 | 2020-04-28 | 上海应用技术大学 | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof |
| CN112439420A (en) * | 2020-12-03 | 2021-03-05 | 南京航空航天大学 | Preparation method of photo-thermal coupling methanol steam reforming hydrogen production composite catalyst |
| CN114192151A (en) * | 2021-12-03 | 2022-03-18 | 宁波中科科创新能源科技有限公司 | Catalyst for methanol steam reforming hydrogen production synthesized by PCVD method and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462967A (en) * | 2009-01-15 | 2009-06-24 | 青岛科技大学 | Method for converting arylamine polyhalide |
| 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 |
| CN103347607A (en) * | 2010-08-25 | 2013-10-09 | 拜耳知识产权有限责任公司 | Catalyst and method for the production of chlorine by gas phase oxidation |
| CN103816921A (en) * | 2014-01-29 | 2014-05-28 | 上海摩醇动力技术有限公司 | Catalyst for hydrogen production via methanol steam reforming as well as preparing method and hydrogen production method thereof |
| CN104645999A (en) * | 2015-02-12 | 2015-05-27 | 上海摩醇动力技术有限公司 | Preparation process for catalyst for hydrogen production through methanol steam reforming |
| US20160024392A1 (en) * | 2014-07-24 | 2016-01-28 | Exxonmobil Chemical Patents Inc. | Production of Xylenes From Syngas |
| CN105536790A (en) * | 2015-12-15 | 2016-05-04 | 上海应用技术学院 | Catalyst for hydrogen production from steam reforming of methanol and preparation method thereof |
| CN108380222A (en) * | 2018-03-08 | 2018-08-10 | 大连大学 | A kind of method and its application of fixed noble metal catalyst active component |
-
2018
- 2018-12-17 CN CN201811544210.1A patent/CN109603834A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101462967A (en) * | 2009-01-15 | 2009-06-24 | 青岛科技大学 | Method for converting arylamine polyhalide |
| CN103347607A (en) * | 2010-08-25 | 2013-10-09 | 拜耳知识产权有限责任公司 | Catalyst and method for the production of chlorine by gas phase oxidation |
| CN103816921A (en) * | 2014-01-29 | 2014-05-28 | 上海摩醇动力技术有限公司 | Catalyst for hydrogen production via methanol steam reforming as well as preparing method and hydrogen production method thereof |
| US20160024392A1 (en) * | 2014-07-24 | 2016-01-28 | Exxonmobil Chemical Patents Inc. | Production of Xylenes From Syngas |
| CN104645999A (en) * | 2015-02-12 | 2015-05-27 | 上海摩醇动力技术有限公司 | Preparation process for catalyst for hydrogen production through methanol steam reforming |
| CN105536790A (en) * | 2015-12-15 | 2016-05-04 | 上海应用技术学院 | Catalyst for hydrogen production from steam reforming of methanol and preparation method thereof |
| CN108380222A (en) * | 2018-03-08 | 2018-08-10 | 大连大学 | A kind of method and its application of fixed noble metal catalyst active component |
Non-Patent Citations (1)
| Title |
|---|
| 李永红等，: ""低温高活性甲醇水蒸气重整制氢催化剂的研究"", 《天然气化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068681A (en) * | 2019-11-28 | 2020-04-28 | 上海应用技术大学 | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof |
| CN112439420A (en) * | 2020-12-03 | 2021-03-05 | 南京航空航天大学 | Preparation method of photo-thermal coupling methanol steam reforming hydrogen production composite catalyst |
| CN114192151A (en) * | 2021-12-03 | 2022-03-18 | 宁波中科科创新能源科技有限公司 | Catalyst for methanol steam reforming hydrogen production synthesized by PCVD method and preparation method thereof |
| CN114192151B (en) * | 2021-12-03 | 2024-02-09 | 宁波中科科创新能源科技有限公司 | Catalyst for preparing hydrogen by reforming methanol steam synthesized by PCVD method and preparation method thereof |
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