CN105233815B - A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen and application - Google Patents
A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen and application Download PDFInfo
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Abstract
Production technology and application the invention discloses a kind of methanol steam high temperature reformation catalyst for preparing hydrogen, the present invention manufactures catalyst carrier with boehmite, titanium dioxide, citric acid and graphite as raw material, and carrier is pressed into Raschig ring shape, it is applicable to the methanol steam high temperature reformation hydrogen production reaction that reaction condition is 300~600 DEG C；Beneficial effects of the present invention are：Catalyst of the invention does not use noble metal catalyst, and does not select traditional coprecipitation method, a large amount of cost-effective and resources, with application value realistic；Catalyst of the invention uses Raschig ring profile, and catalyst specific surface is bigger, and mass transfer, heat-transfer effect are more preferable；Catalyst application of the present invention is simple, and reactor directly is warmed up into temperature in use, enters unstripped gas and can be used, and is released without mechanical water in temperature-rise period, and catalyst volume shrinks small.
Description
Technical field
The present invention relates to chemical field, more particularly to a kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen
And application.
Background technology
Methyl alcohol has that cheap and easy to get, energy density is high, and carbon content is low, and transport and the advantage such as storage is convenient, is described as
It is that most promising height takes energy fuel；Its reforming hydrogen manufacturing mode mainly includes Direct Pyrolysis, steam reformation and partial oxidation weight
Whole three kinds, wherein Methanol cluster hydrogen manufacturing be conversion gas in hydrogen content highest reaction, with low cost, mild condition,
The advantages of product component is few easily separated.
The core of Methanol cluster hydrogen producing technology is catalyst, and relevant catalyst has obtained extensive, deep grinding
Study carefully, wherein study in the majority with copper-based catalysts, but copper-based catalysts are primarily adapted for use in 210 ~ 300 DEG C of low temperature environment, and it is uncomfortable
For the hot environment of 300 ~ 550 DEG C of small-sized movable hydrogen producer and fuel cell required for.In recent years, it is adaptable to high
The catalyst of warm environment hydrogen manufacturing, main research concentrates on Zn-Cr catalyst and noble metal catalyst, although noble metal catalyst has
There are greater activity and stabilization and receive much concern, but its expensive price is still difficult in adapt to present hydrogen manufacturing market needs.Cao Weiqiang,
Chen Guangwen etc. is catalyzed journal 10 in document（2006）In the non-noble metal Zn-Cr catalyst that refers to, patent 00110041.6 carries
And with ZnO as active component, VIII race's part metals for coagent catalyst non-precious metal catalyst, its preparation method
All it is to use co-precipitation technology of preparing, this preparation method typically selects sodium carbonate as coprecipitator, and is co-precipitated
During requirement to pH value it is higher, while wash precipitated filter cakes to need to consume substantial amounts of water；Such waste water resource, and cause
Substantial amounts of waste water needs treatment, not only uneconomical but also not environmentally, it is often more important that, still there is part sodium ion to be difficult in catalyst thorough
Bottom washes clean, influences the service life of catalyst.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency in the presence of prior art, there is provided a kind of methanol steam high temperature
Reforming hydrogen-production catalyst, it does not use noble metal catalyst, has saved cost, and does not select traditional coprecipitation method, section
About water resource, the service life for reducing wastewater discharge, extending catalyst, with practicality very high.
In order to realize foregoing invention purpose, the invention provides following technical scheme：
A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen, it is characterised in that it is comprised the following steps：
（1）The preparation of titania modified alumina support：Boehmite, titanium dioxide, citric acid and graphite are made
It is raw material, is mixed to form mixed material, the mass ratio of the boehmite, titanium dioxide, citric acid and graphite is：Intend thin water
Aluminium stone 85~90, titanium dioxide 6~8, citric acid 1.5~3, graphite 2~4；The mixed material be milled to granularity for 200~
Added water after 350 mesh and mix and granulate, mixed material is with the mass ratio of water：Mixed material 100, water 20~40, mix after granulation
The granularity of material is 8~12 mesh, then that the mixed material after granulation is compressing, and is 0.6~0.9MPa by pressure value
6~12h of steam treatment, then 700~850 DEG C calcine 8~10h be made titania modified alumina support；
（2）The configuration of catalyst activity component and coagent solution：By zinc nitrate, chromic nitrate, lanthanum nitrate be dissolved in from
Nitric acid metal mixed salt solution is made in sub- water, the mass ratio of each oxide is in the nitric acid slaine：Zinc oxide 75~85,
Chromium oxide 10~20, lanthana 0~5；The total concentration of the nitric acid metal mixed salt solution is 3 ~ 4mol/L；
（3）The load of catalyst activity component and auxiliary agent：By step under the conditions of 60~80 DEG C（1）Prepared titanium dioxide
Titanium modified aluminium oxide supports finished product impregnated in step（2）In the nitric acid metal mixed salt solution of preparation, dip time is controlled 30
~60min, dipping completes, after 120~140 DEG C of 2~6h of drying, to be placed after then calcining 3~7h under the conditions of 450~550 DEG C
Cooling；
（4）According to step（3）Method repeated impregnations, drying, calcining, cooling 2~4 times until finished product, oxygen in catalyst
Change zinc, chromium oxide, the gross weight of lanthana and account for the 30~40% of catalyst gross mass, obtain final product methanol steam high temperature reformation hydrogen manufacturing
Catalyst.
Preferably, the material after the granulation is compressing, and it is shaped as Raschig ring.
Preferably, the Raschig ring size is：2~3mm of external diameter, 2~3mm of height, 1~1.5mm of internal diameter.
A kind of application of methanol steam high temperature reformation catalyst for preparing hydrogen, it is characterised in that by methanol steam high temperature weight
Whole catalyst for preparing hydrogen is fitted into reactor, then heats up, and the temperature of reactor is kept for 300~600 DEG C, then by methyl alcohol and water
The mixed gas of steam are passed through reactor after being warming up to 200~250 DEG C, carry out catalytic reaction；Reacted mixed gas are through cold
Solidifying, collection obtains the final product rich in hydrogen.
Preferably, the temperature of the reactor is kept for 350~500 DEG C.
Preferably, described methyl alcohol is with the mol ratio of vapor：Methyl alcohol 1.0, water 0.5~3.0；The reaction pressure of reactor
Power is 0.1~3.0MPa.
Preferably, the use condition of described methanol steam high temperature reformation catalyst for preparing hydrogen is：Methyl alcohol and water mole
Than for：Methyl alcohol 1.0, water 1.5~2.0, reaction pressure are 0.1~2.0MPa.
Compared with prior art, beneficial effects of the present invention：
1st, catalyst of the invention does not use noble metal catalyst, and does not select traditional coprecipitation method, great Liang Jie
About cost and resource, with application value realistic.
2nd, catalyst of the invention uses Raschig ring profile, and catalyst specific surface is bigger, and mass transfer, heat-transfer effect are more preferable.
3rd, catalyst application of the present invention is simple, is directly warmed up to temperature in use, enters unstripped gas and can be used, in temperature-rise period
Released without mechanical water, catalyst volume shrinks small.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
For the scope of above-mentioned theme of the invention is only limitted to following embodiment, all technologies realized based on present invention belong to this
The scope of invention.
Embodiment 1
A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen, it is comprised the following steps：Thin water aluminium will be intended
Stone, titanium dioxide, citric acid and graphite are mixed to form mixed material, the boehmite, titanium dioxide, lemon as raw material
Lemon acid and the mass ratio of graphite are：Boehmite 85, titanium dioxide 6, citric acid 1.5, graphite 2；The mixed material ball milling
Added water after being 200 mesh to granularity and mix and granulate, mixed material is with the mass ratio of water：Mixed material 100, water 20, after granulation
The granularity of mixed material is 8 mesh, and then that the mixed material after granulation is compressing, it is shaped as Raschig ring, the Raschig ring
Size is：External diameter 2mm, height 2mm, internal diameter 1mm；The mixed material of the shaping is the steam treatment of 0.6Mpa by pressure value
12h, then calcines 8h and is made titania modified alumina support at 700 DEG C；Zinc nitrate, chromic nitrate, lanthanum nitrate are dissolved in
Nitric acid metal mixed salt solution is made in ionized water, zinc oxide, chromium oxide, the mass ratio of lanthana in the nitric acid slaine
For：Zinc oxide 75, chromium oxide 20, lanthana 5；The total concentration of the nitric acid metal mixed solution is 3mol/L；Catalyst activity
The load of component and auxiliary agent：The titania modified alumina support finished product for preparing impregnated in the nitre of preparation under the conditions of 60 DEG C
In acid metal salt mixed solution, in 30min, dipping completes to dry 2h after 120 DEG C, then in 450 DEG C of bars for dip time control
Cooling is placed after 3h is calcined under part；Repeated impregnations, drying, calcining, cooling 2 times are until finished product, zinc oxide, oxidation in catalyst
Chromium, the gross weight of lanthana account for the 30% of catalyst gross mass, obtain final product methanol steam high temperature reformation catalyst for preparing hydrogen, its physics
Index is：Water pore volume is 55 ~ 60 %, specific surface >=100 m2/ g, intensity >=180 N/, carrier heap density is 0.65 ~ 0.70
kg/L.Obtained methanol steam high temperature reformation catalyst for preparing hydrogen is fitted into reactor, the reactor is 25 × 3 × 60mm
Stainless steel tubular reactor, the catalyst amount of filling out be 30mL, be then that medium is heated up with air or nitrogen, heat up
To reaction temperature, the speed control of intensification is 20 DEG C/h, and reaction temperature remains 300 DEG C, then by methyl alcohol and the mixed liquor of water
Body is passed through steam generator, is warming up to after 200 DEG C and is changed into the mixed gas of methanol vapor and vapor, and the methyl alcohol rubs with water
You are at ratio：Methyl alcohol 1.0, water 0.5~3.0, the present embodiment methyl alcohol are preferably with the mol ratio of water：Methyl alcohol 1.0, water 1.7；The first
Alcohol is controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor is passed through reactor again with the mixed gas of vapor, carries out
Catalytic reaction, reaction pressure is controlled to 0.1MPa；Reacted mixed gas are condensed, collect the final product for obtaining being rich in hydrogen
Thing.The H of final product is measured through Agilent-6890N GC gas chromatographs2Content is that the content of 74.53%, CO is 1.2%,
The conversion ratio of methyl alcohol is 97%.
Co-precipitation methanol steam catalyst for preparing hydrogen purchased in market is fitted into reactor, the reactor be 25 × 3 ×
The stainless steel tubular reactor of 60mm, the catalyst amount of filling out is 30mL, is then that medium is heated up with air or nitrogen,
Reaction temperature is warming up to, the speed control of intensification is 20 DEG C/h, and reaction temperature remains 300 DEG C, then that methyl alcohol is mixed with water
Close liquid and be passed through steam generator, be warming up to after 200 DEG C and be changed into the mixed gas of methanol vapor and vapor, the methyl alcohol and water
Mol ratio be：Methyl alcohol 1.0, water 1.7, the methyl alcohol are controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor and water
The mixed gas of steam are passed through reactor again, carry out catalytic reaction, and reaction pressure is controlled to 0.1MPa；Reacted mixed gas
Condensed, collection obtains the final product rich in hydrogen.Final product is measured through Agilent-6890N GC gas chromatographs
H2Content is that the content of 73.75%, CO is 1.7%, and the conversion ratio of methyl alcohol is 93%.
Embodiment 2
A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen, it is comprised the following steps：Thin water aluminium will be intended
Stone, titanium dioxide, citric acid and graphite are mixed to form mixed material, the boehmite, titanium dioxide, lemon as raw material
Lemon acid and the mass ratio of graphite are：Boehmite 90, titanium dioxide 6, citric acid 1.5, graphite 2；The mixed material ball milling
Added water after being 350 mesh to granularity and mix and granulate, mixed material is with the mass ratio of water：Mixed material 100, water 30, after granulation
The granularity of mixed material is 12 mesh, and then that the mixed material after granulation is compressing, it is shaped as Raschig ring, the Raschig ring
Size is：External diameter 3mm, height 3mm, internal diameter 1.5mm；The mixed material of the shaping by pressure value for 0.9Mpa steam at
Reason 12h, then calcines 10h and is made titania modified alumina support at 850 DEG C；Zinc nitrate, chromic nitrate, lanthanum nitrate are dissolved in
Nitric acid metal mixed salt solution is made in deionized water, zinc oxide, chromium oxide, the mass ratio of lanthana in the nitric acid slaine
For：Zinc oxide 85, chromium oxide 10, lanthana 5；The total concentration of the nitric acid metal mixed salt solution is 4 mol/L；Catalyst is lived
The load of property component and auxiliary agent：The titania modified alumina support finished product for preparing be impregnated in into preparation under the conditions of 80 DEG C
In nitric acid metal mixed salt solution, in 60 min, dipping completes to dry 6h after 140 DEG C, then 550 for dip time control
Cooling is placed after 7h is calcined under the conditions of DEG C；Repeated impregnations, drying, calcining, cooling 4 times are until finished product, zinc oxide, oxygen in catalyst
Change chromium, the gross weight of lanthana and account for the 40% of catalyst gross mass, obtain final product methanol steam high temperature reformation catalyst for preparing hydrogen, its thing
Managing index is：Water pore volume is 55 ~ 60 %, specific surface >=100 m2/ g, intensity >=180 N/, carrier heap density be 0.65 ~
0.70 kg/L.Obtained methanol steam high temperature reformation catalyst for preparing hydrogen is fitted into reactor, the reactor is 25 × 3
The stainless steel tubular reactor of × 60mm, the catalyst amount of filling out is 30mL, is then that medium is risen with air or nitrogen
Temperature, is warming up to reaction temperature, and the speed control of intensification is 30 DEG C/h, and reaction temperature remains 600 DEG C, then by methyl alcohol and water
Mixing liquid is passed through steam generator, is warming up to after 250 DEG C and is changed into the mixed gas of methanol vapor and vapor, the methyl alcohol with
The mol ratio of water is：Methyl alcohol 1.0, water 0.5~3.0, the present embodiment methyl alcohol are preferably with the mol ratio of water：Methyl alcohol 1.0, water 1.7；
The methyl alcohol is controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor is passed through reaction again with the mixed gas of vapor
Device, carries out catalytic reaction, and reaction pressure is controlled to 2.0MPa；Reacted mixed gas are condensed, collection is obtained rich in hydrogen
Final product.The H of final product is measured through Agilent-6890N GC gas chromatographs2Content is the content of 74.91%, CO
It is 1.9%, the conversion ratio of methyl alcohol is 96%.
Co-precipitation methanol steam catalyst for preparing hydrogen purchased in market is fitted into reactor, the reactor be 25 × 3 ×
The stainless steel tubular reactor of 60mm, the catalyst amount of filling out is 30 mL, is then that medium is risen with air or nitrogen
Temperature, is warming up to reaction temperature, and the speed control of intensification is 30 DEG C/h, and reaction temperature remains 600 DEG C, then by methyl alcohol and water
Mixing liquid is passed through steam generator, is warming up to after 250 DEG C and is changed into the mixed gas of methanol vapor and vapor, the methyl alcohol with
The mol ratio of water is：Methyl alcohol 1.0, water 1.7, the methyl alcohol are controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor with
The mixed gas of vapor are passed through reactor again, carry out catalytic reaction, and reaction pressure is controlled to 2.0MPa；Reacted gaseous mixture
Body is condensed, collect the final product for obtaining being rich in hydrogen.Final product is measured through Agilent-6890N GC gas chromatographs
H2Content is that the content of 73.29%, CO is 2.4%, and the conversion ratio of methyl alcohol is 90%.
Embodiment 3
A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen, it is comprised the following steps：Thin water aluminium will be intended
Stone, titanium dioxide, citric acid and graphite are mixed to form mixed material, the boehmite, titanium dioxide, lemon as raw material
Lemon acid and the mass ratio of graphite are：Boehmite 88, titanium dioxide 7, citric acid 2.2, graphite 3；The mixed material ball milling
Added water after being 300 mesh to granularity and mix and granulate, mixed material is with the mass ratio of water：Mixed material 100, water 40, after granulation
The granularity of mixed material is 10 mesh, and then that the mixed material after granulation is compressing, it is shaped as Raschig ring, the Raschig ring
Size is：External diameter 2.5mm, height 2.5mm, the 2mm of internal diameter 1.；The mixed material of the shaping is 0.75Mpa's by pressure value
Steam treatment 9h, then calcines 9h and is made titania modified alumina support at 780 DEG C；By zinc nitrate, chromic nitrate, lanthanum nitrate
It is dissolved in deionized water and is made nitric acid metal mixed salt solution, zinc oxide, chromium oxide, the matter of lanthana in the nitric acid slaine
Measuring ratio is：Zinc oxide 80, chromium oxide 17, lanthana 3；The total concentration of the nitric acid metal mixed salt solution is 3.5mol/L；Urge
The load of agent active component and auxiliary agent：The titania modified alumina support finished product for preparing impregnated under the conditions of 70 DEG C
In the nitric acid metal mixed salt solution of preparation, in 45 min, dipping completes to dry 4h after 130 DEG C, then for dip time control
Cooling is placed after calcining 5h under the conditions of 500 DEG C；Repeated impregnations, drying, calcining, cooling 3 times are until finished product, aoxidizes in catalyst
Zinc, chromium oxide, the gross weight of lanthana account for the 35% of catalyst gross mass, obtain final product methanol steam high temperature reformation catalyst for preparing hydrogen,
Its physical index is：Water pore volume is 55 ~ 60 %, specific surface >=100 m2/ g, intensity >=180 N/, carrier heap density is 0.65
~0.70 kg/L.Obtained methanol steam high temperature reformation catalyst for preparing hydrogen is fitted into reactor, the reactor is 25 × 3
The stainless steel tubular reactor of × 60mm, the catalyst amount of filling out is 30mL, is then that medium is risen with air or nitrogen
Temperature, is warming up to reaction temperature, and the speed control of intensification is 25 DEG C/h, and reaction temperature remains 500 DEG C, then by methyl alcohol and water
Mixing liquid is passed through steam generator, is warming up to after 225 DEG C and is changed into the mixed gas of methanol vapor and vapor, the methyl alcohol with
The mol ratio of water is：Methyl alcohol 1.0, water 0.5~3.0, the present embodiment methyl alcohol are preferably with the mol ratio of water：Methyl alcohol 1.0, water 1.7；
The methyl alcohol is controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor is passed through reaction again with the mixed gas of vapor
Device, carries out catalytic reaction, and reaction pressure is controlled to 1.5MPa；Reacted mixed gas are condensed, collection is obtained rich in hydrogen
Final product.The H of final product is measured through Agilent-6890N GC gas chromatographs2Content is the content of 74.65%, CO
It is 1.6%, the conversion ratio of methyl alcohol is 98%.
Co-precipitation methanol steam catalyst for preparing hydrogen purchased in market is fitted into reactor, the reactor be 25 × 3 ×
The stainless steel tubular reactor of 60mm, the catalyst amount of filling out is 30mL, is then that medium is heated up with air or nitrogen,
Reaction temperature is warming up to, the speed control of intensification is 25 DEG C/h, and reaction temperature remains 500 DEG C, then that methyl alcohol is mixed with water
Close liquid and be passed through steam generator, be warming up to after 225 DEG C and be changed into the mixed gas of methanol vapor and vapor, the methyl alcohol and water
Mol ratio be：Methyl alcohol 1.0, water 1.7, the methyl alcohol are controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor and water
The mixed gas of steam are passed through reactor again, carry out catalytic reaction, and reaction pressure is controlled to 1.5MPa；Reacted mixed gas
Condensed, collection obtains the final product rich in hydrogen.Final product is measured through Agilent-6890N GC gas chromatographs
H2Content is that the content of 73.35%, CO is 2.1%, and the conversion ratio of methyl alcohol is 92%.
Embodiment 4
A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen, it is comprised the following steps：Thin water aluminium will be intended
Stone, titanium dioxide, citric acid and graphite are mixed to form mixed material, the boehmite, titanium dioxide, lemon as raw material
Lemon acid and the mass ratio of graphite are：Boehmite 90, titanium dioxide 6, citric acid 1.5, graphite 4；The mixed material ball milling
Added water after being 200 mesh to granularity and mix and granulate, mixed material is with the mass ratio of water：Mixed material 100, water 20, after granulation
The granularity of mixed material is 8 mesh, and then that the mixed material after granulation is compressing, it is shaped as Raschig ring, the Raschig ring
Size is：External diameter 2mm, height 2mm, internal diameter 1mm；The mixed material of the shaping is the steam treatment of 0.6Mpa by pressure value
8h, then calcines 8 h and is made titania modified alumina support at 720 DEG C；Zinc nitrate, chromic nitrate, lanthanum nitrate are dissolved in
Nitric acid metal mixed salt solution is made in ionized water, zinc oxide, chromium oxide, the mass ratio of lanthana in the nitric acid slaine
For：Zinc oxide 85, chromium oxide 15, lanthana 0；The total concentration of the nitric acid metal mixed salt solution is 3mol/L；Catalyst is lived
The load of property component and auxiliary agent：The titania modified alumina support finished product for preparing be impregnated in into preparation under the conditions of 60 DEG C
In nitric acid metal mixed salt solution, in 30min, dipping completes to dry 6h after 120 DEG C, then at 550 DEG C for dip time control
Under the conditions of calcine 3h after place cooling；Repeated impregnations, drying, calcining, cooling 3 times are until finished product, zinc oxide, oxidation in catalyst
Chromium, the gross weight of lanthana account for the 32% of catalyst gross mass, obtain final product methanol steam high temperature reformation catalyst for preparing hydrogen, its physics
Index is：Water pore volume is 55 ~ 60 %, specific surface >=100 m2/ g, intensity >=180 N/, carrier heap density is 0.65 ~ 0.70
kg/L.Obtained methanol steam high temperature reformation catalyst for preparing hydrogen is fitted into reactor, the reactor is 25 × 3 × 60mm
Stainless steel tubular reactor, the catalyst amount of filling out be 30mL, be then that medium is heated up with air or nitrogen, heat up
To reaction temperature, the speed control of intensification is 30 DEG C/h, and reaction temperature remains 350 DEG C, then by methyl alcohol and the mixed liquor of water
Body is passed through steam generator, is warming up to after 250 DEG C and is changed into the mixed gas of methanol vapor and vapor, and the methyl alcohol rubs with water
You are at ratio：Methyl alcohol 1.0, water 0.5~3.0, the present embodiment methyl alcohol are preferably with the mol ratio of water：Methyl alcohol 1.0, water 1.7；The first
Alcohol is controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor is passed through reactor again with the mixed gas of vapor, carries out
Catalytic reaction, reaction pressure is controlled to 3.0MPa；Reacted mixed gas are condensed, collect the final product for obtaining being rich in hydrogen
Thing.The H of final product is measured through Agilent-6890N GC gas chromatographs2Content is that the content of 74.37%, CO is 1.4%,
The conversion ratio of methyl alcohol is 98%.
Co-precipitation methanol steam catalyst for preparing hydrogen purchased in market is fitted into reactor, the reactor be 25 × 3 ×
The stainless steel tubular reactor of 60mm, the catalyst amount of filling out is 30mL, is then that medium is heated up with air or nitrogen,
Reaction temperature is warming up to, the speed control of intensification is 30 DEG C/h, and reaction temperature remains 350 DEG C, then that methyl alcohol is mixed with water
Close liquid and be passed through steam generator, be warming up to after 250 DEG C and be changed into the mixed gas of methanol vapor and vapor, the methyl alcohol and water
Mol ratio be：Methyl alcohol 1.0, water 1.7, the methyl alcohol are controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor and water
The mixed gas of steam are passed through reactor again, carry out catalytic reaction, and reaction pressure is controlled to 3.0MPa；Reacted mixed gas
Condensed, collection obtains the final product rich in hydrogen.Final product is measured through Agilent-6890N GC gas chromatographs
H2Content is that the content of 73.51%, CO is 2.1%, and the conversion ratio of methyl alcohol is 91%.
Embodiment 5
A kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen, it is comprised the following steps：Thin water aluminium will be intended
Stone, titanium dioxide, citric acid and graphite are mixed to form mixed material, the boehmite, titanium dioxide, lemon as raw material
Lemon acid and the mass ratio of graphite are：Boehmite 85, titanium dioxide 8, citric acid 3, graphite 4；The mixed material is milled to
Granularity is mixed and granulated to be added water after 350 mesh, and mixed material is with the mass ratio of water：Mixed material 100, water 35, mix after granulation
The granularity of compound material is 11 mesh, and then that the mixed material after granulation is compressing, it is shaped as Raschig ring, the Raschig ring chi
It is very little to be：External diameter 2.5mm, height 3mm, internal diameter 1.5mm；The mixed material of the shaping by pressure value for 0.8Mpa steam at
Reason 10h, then calcines 10 h and is made titania modified alumina support at 850 DEG C；Zinc nitrate, chromic nitrate, lanthanum nitrate is molten
Nitric acid metal mixed salt solution is made in deionized water, zinc oxide, chromium oxide, the quality of lanthana in the nitric acid slaine
Than for：Zinc oxide 85, chromium oxide 20, lanthana 2；The total concentration of the nitric acid metal mixed salt solution is 4mol/L；Catalyst
The load of active component and auxiliary agent：The titania modified alumina support finished product for preparing be impregnated in into preparation under the conditions of 70 DEG C
Nitric acid metal mixed salt solution in, in 40 min, dipping completes to dry 3h after 140 DEG C, then 530 for dip time control
Cooling is placed after 6 h are calcined under the conditions of DEG C；Repeated impregnations, drying, calcining, cooling 2 times until finished product, zinc oxide in catalyst,
Chromium oxide, the gross weight of lanthana account for the 39% of catalyst gross mass, obtain final product methanol steam high temperature reformation catalyst for preparing hydrogen, its
Physical index is：Water pore volume is 55 ~ 60 %, specific surface >=100 m2/ g, intensity >=180 N/, carrier heap density be 0.65 ~
0.70 kg/L.Obtained methanol steam high temperature reformation catalyst for preparing hydrogen is fitted into reactor, the reactor is 25 × 3
The stainless steel tubular reactor of × 60mm, the catalyst amount of filling out is 30mL, is then that medium is risen with air or nitrogen
Temperature, is warming up to reaction temperature, and the speed control of intensification is 29 DEG C/h, and reaction temperature remains 450 DEG C, then by methyl alcohol and water
Mixing liquid is passed through steam generator, is warming up to after 240 DEG C and is changed into the mixed gas of methanol vapor and vapor, the methyl alcohol with
The mol ratio of water is：Methyl alcohol 1.0, water 0.5~3.0, the present embodiment methyl alcohol are preferably with the mol ratio of water：Methyl alcohol 1.0, water 1.7；
The methyl alcohol is controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor is passed through reaction again with the mixed gas of vapor
Device, carries out catalytic reaction, and reaction pressure is controlled to 1.0MPa；Reacted mixed gas are condensed, collection is obtained rich in hydrogen
Final product.The H of final product is measured through Agilent-6890N GC gas chromatographs2Content is the content of 74.86%, CO
It is 1.7%, the conversion ratio of methyl alcohol is 99%.
Co-precipitation methanol steam catalyst for preparing hydrogen purchased in market is fitted into reactor, the reactor be 25 × 3 ×
The stainless steel tubular reactor of 60mm, the catalyst amount of filling out is 30mL, is then that medium is heated up with air or nitrogen,
Reaction temperature is warming up to, the speed control of intensification is 29 DEG C/h, and reaction temperature remains 450 DEG C, then that methyl alcohol is mixed with water
Close liquid and be passed through steam generator, be warming up to after 240 DEG C and be changed into the mixed gas of methanol vapor and vapor, the methyl alcohol and water
Mol ratio be：Methyl alcohol 1.0, water 1.7, the methyl alcohol are controlled to 1.0h with the mixing liquid liquid air speed of water-1；Methanol vapor and water
The mixed gas of steam are passed through reactor again, carry out catalytic reaction, and reaction pressure is controlled to 1.0MPa；Reacted mixed gas
Condensed, collection obtains the final product rich in hydrogen.Final product is measured through Agilent-6890N GC gas chromatographs
H2Content is that the content of 73.41%, CO is 2.2%, and the conversion ratio of methyl alcohol is 92%.
As seen from the above embodiment, the methanol steam high temperature weight that under 300~600 DEG C of reaction temperature prepared by the present invention
The catalytic performance of whole catalyst for preparing hydrogen is better than methanol steam catalyst for preparing hydrogen prepared by traditional co-precipitation method.
Claims (3)
1. a kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen, it is characterised in that it is comprised the following steps：
（1）The preparation of titania modified alumina support：Using boehmite, titanium dioxide, citric acid and graphite as original
Material, is mixed to form mixed material, and the mass ratio of the boehmite, titanium dioxide, citric acid and graphite is：Boehmite
85~90, titanium dioxide 6~8, citric acid 1.5~3, graphite 2~4；The mixed material is milled to granularity for 200~350 mesh
After add water and mix and granulate, mixed material is with the mass ratio of water：Mixed material 100, water 20~40, mixed material after granulation
Granularity is 8~12 mesh, then that the mixed material after granulation is compressing, and by steam that pressure value is 0.6~0.9MPa
6~12h for the treatment of, then calcines 8~10h and is made titania modified alumina support at 700~850 DEG C；
（2）The configuration of catalyst activity component and coagent solution：Zinc nitrate, chromic nitrate, lanthanum nitrate are dissolved in deionized water
In be made nitric acid metal mixed salt solution, the mass ratio of each oxide is in the nitric acid slaine：Zinc oxide 75~85, oxidation
Chromium 10~20, lanthana 0~5；The total concentration of the nitric acid metal mixed salt solution is 3~4mol/L；
（3）The load of catalyst activity component and auxiliary agent：By step under the conditions of 60~80 DEG C（1）Prepared titanium dioxide changes
Property alumina support impregnated in step（2）In the nitric acid metal mixed salt solution of preparation, dip time is controlled in 30~60min,
Dipping completes, after 120~200 DEG C of 2~6h of drying, cooling to be placed after then calcining 3~10h under the conditions of 450~550 DEG C；
（4）According to step（3）Method repeated impregnations, drying, calcining, cooling 2~4 times until finished product, zinc oxide in catalyst,
Chromium oxide, the gross weight of lanthana account for the 30~40% of catalyst gross mass, obtain final product methanol steam high temperature reformation producing hydrogen, catalyzing
Agent.
2. a kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen according to claim 1, its feature exists
In the material after the granulation is compressing, and it is shaped as Raschig ring.
3. a kind of production technology of methanol steam high temperature reformation catalyst for preparing hydrogen according to claim 2, its feature exists
In the Raschig ring size is：2~3mm of external diameter, 2~3mm of height, 1~1.5mm of internal diameter.
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