CN106076353A - A kind of monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour - Google Patents
A kind of monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour Download PDFInfo
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- CN106076353A CN106076353A CN201610651673.2A CN201610651673A CN106076353A CN 106076353 A CN106076353 A CN 106076353A CN 201610651673 A CN201610651673 A CN 201610651673A CN 106076353 A CN106076353 A CN 106076353A
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- Prior art keywords
- catalyst
- water vapour
- preparing hydrogen
- hydrogen
- reforming methanol
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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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour, main chemical compositions is by CuO, ZnO, Al2O3、Cr2O3、CeO2And the composition such as auxiliary agent is constituted；Wherein CuO (65%), ZnO (8%), Al2O3(≧8%).Catalyst production process includes batch mixing, mediates, filters, extruded, aging, dry, roasting, cuts and pack.It is mainly characterized by it is characterized in that for the shape of catalyst for preparing hydrogen by reforming methanol and water vapour is cellular and the production of catalyst uses monolithic extruded molding.
Description
Technical field
The invention belongs to chemical industry and new energy field, relate to a kind of catalyst for preparing hydrogen by reforming methanol and water vapour and producer thereof
Method.
Background technology
Hydrogen Energy is considered 21 century the most potential clean energy resource, and Hydrogen Energy application was just produced before 200 years by the mankind
Interest, since 20 century 70s, Hydrogen Energy research has the most extensively been carried out in many countries and regions in the world.As far back as 1970
Year, the Technical Research Center of General Motors Overseas Corporation just proposes the concept of " hydrogen economy ".Since the mid-90 in 20th century
Many factors converge the captivation adding hydrogen economy.These factors include: lasting urban air pollution, to relatively low or
The demand of the vehicles of zero waste gas discharge, minimizing are to the foreign country needs of petroleum import, CO2Discharge and Global climate change, storage
Deposit the demand etc. of Reproduceable electricity supply.The research and development of Hydrogen Energy can be traced back to early 1960s by China, China
Scientist is the aerospace industry of development this country, production, the H to the liquid hydrogen as rocket fuel2/O2The development of fuel cell with open
Send out and carried out working in a large number and effectively.Hydrogen is developed as energy carrier and new energy resource system, is then from 20th century
The seventies starts.Now, for developing Hydrogen Energy further, promoting the development of hydrogen utilization, Hydrogen Technology has been put into China ten
Three or five energy development planning.
The method of hydrogen manufacturing at present has water electrolysis hydrogen production, water gas hydrogen manufacturing, oil gas hydrogen manufacturing, natural gas hydrogen preparation and methanol
Hydrogen manufacturing etc..Wherein hydrogen from methyl alcohol is the hydrogen producing technology of a kind of economical and effective, technology maturation.
Methanol is the bulk raw material of a kind of wide material sources, have that energy density is big, carbon content is low, store and transport convenient etc.
Feature is it is considered to be most promising height takes energy fuel.Methanol, through being catalytically conveted to hydrogen, can meet on-the-spot under more occasion using
The demand of hydrogen, solves hydrogen transport, the problem of storage difficulty.
It is the main of hydrogen from methyl alcohol that the oxidation of methanol decomposition, methanol steam reforming, methanol fractions and methanol oxidative steam are reformed
Method.In hydrogen from methyl alcohol method, most study is Methanol cluster (SRM) hydrogen manufacturing.Methanol steam reforming hydrogen manufacturing by
In hydrogen yield high (close to 75%), reasonable energy utilization, process control is simple, it is simple to industrial operation and be used more.Methanol
One of key of hydrogen manufacturing core technology is the hydrogen production reaction catalyst of exploitation function admirable.
The catalyst being applied to preparing hydrogen by reforming methanol at present mainly has two classes: a class is non-precious metal catalyst, mainly wraps
Include copper-based catalysts (such as CuO/ZnO/Al2O3、CuO/ZnO/ZrO2Deng) and non-copper-based catalysts (such as Zn-Cr etc.)；Another kind of it is
Noble metal catalyst, typical representative is Pd/ZnO catalyst.
Hydrogen from methyl alcohol catalyst research comparative maturity is Pd system noble metal catalyst and Cu series catalysts.In recent years, a lot
It is also widely used for methanol catalytically reforming hydrogen producing reaction system about noble metal catalysts such as palladium, platinum, rhodiums.Palladium series catalyst
Feature is that catalyst stability is good, is affected little by poisonous substance and heat, but activity is not as Cu-series catalyst, generates CO after reforming reaction
Content is of a relatively high.Iwasa etc. have studied catalytic reforming methanol oxygen making reaction activity on the catalyst such as Ni, Pd, Pt and Rh, sends out
The performance of existing catalyst is closely related with the reactivity worth of the formic acid species of formation in course of reaction, wherein Pd/ZnO and Pt/ZnO
Catalysis activity the highest.Compared with noble metal catalyst, the low-temperature reformate activity of copper-based catalysts is preferable, under appropriate conditions
Oxygen and carbon dioxide can be generated by highly selective, be applied to methanol steam reforming atmosphere technology the most widely.
It is presently used for business-like CuO/ZnO/Al2O3Catalyst is good hydrogen from methyl alcohol catalyst it can also be used to close
Become in the catalytic reaction of methanol, and show superior catalytic performance.Copper-based catalysts includes CuO/Al2O3、CuO/ZnO、CuO/
ZrO2、CuO/CeO2、CuO/SiO2、CuO/ZnO/Al2O3、CuO/ZnO/ZrO2、CuO/ZnO/ZrO2/ Al2O3Deng, cupper-based catalyst
The feature of agent is that reforming temperature is low, can generate CO by highly selective under appropriate conditions2And H2, in reformation tail gas, CO content is relatively
Low.
Most all metal luster cylinders in current commercial catalyst, volume is generally φ about 5 × 5.
This patent announces a kind of monolithic extruded formed honeycomb formula catalyst for preparing hydrogen by reforming methanol and water vapour, has hydrogen production reaction performance
Good, the pressure loss is low, it is easy to the features such as maximization.
Summary of the invention
A kind of methanol steam reforming catalyst, main chemical compositions is by CuO, ZnO, Al2O3、Cr2O3、CeO2And auxiliary agent etc.
Composition is constituted；Wherein CuO (65%), ZnO (8%), Al2O3(≧8%).Catalyst production process by batch mixing, mediate, filter,
Extrusion molding, aging, dry, roasting, cutting and packaging process composition.
(1) batch mixing: the Cu (NO that will prepare3)2·3H2O、A1(NO3)3·9H2O、Zn(NO3)2·6H2O、Cr(NO3)3·
9H2The catalyst precursors such as O are placed in mixing tank.
(2) mediate: add water, binding agent and liquid toner etc. and mediate, need to control slurry in kneading process
PH value, water content and rheological characteristic.Control reaction temperature is at about 70 DEG C, and the pH value of regulation slurry, about 8.0, stirs 2-
3 hours.
(3) filter: discharge the residual air in slurry, improve consistency and the plasticity of slurry.
(4) extrusion molding: use high pressure vacuum extruder to extrude cellular catalyst idiosome.
(5) ageing: place 10-20h below 25 DEG C in environment.
(6) be dried: wet idiosome is put in drying equipment, according to certain heating curve, less than 110 DEG C under the conditions of do
Dry 12h.
(7) roasting: put in roasting apparatus by dried catalyst monomer, according to certain heating curve, at 400 DEG C
Roasting 2-8h under the conditions of below.
(8) cut and pack: according to required requirement, catalyst monomer being cut into certain length, wrapping after inspection
Dress.
A kind of monolithic extruded formed honeycomb formula catalyst for preparing hydrogen by reforming methanol and water vapour shape is shown in Figure of description 1.
It is embodied as case
1 test activity rating condition:
Catalyst volume 250ml
Reaction control temperature 220 DEG C
Reaction controlling pressure 101KPa
H2O/CH3OH(molar ratio) 1.2
GHSV 4000h–1
Embodiment sample 10%H2-N2350 DEG C of prereduction of gaseous mixture 2 hours.
2 experimental techniques
Liquid methanol and H2O micro pump injects, and enters reactor after vaporization, and air velocity uses mass flowmenter to control.
Product forms by gas chromatographic analysis through ice-cold, silica dehydrator, outlet dry gas, and Ar makees carrier gas, and packed column is TDX-01,
Data acquisition chromatographic work station.
3. result
The H of end product is recorded through gas chromatograph2Content be the conversion ratio of 74.88% methanol be 99%.
Claims (5)
1. a monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour, main chemical compositions by CuO, ZnO,
Al2O3、Cr2O3、CeO2And the composition such as auxiliary agent is constituted；Wherein CuO (65%), ZnO (8%), Al2O3(≧8%)。
2. catalyst production process includes batch mixing, mediates, filters, extruded, aging, dry, roasting, cuts and pack.
One the most according to claim 1 monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour, it is special
Levy be for the shape of catalyst for preparing hydrogen by reforming methanol and water vapour be cellular.
One the most according to claim 1 monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour, it is special
Levy and be that the production for catalyst for preparing hydrogen by reforming methanol and water vapour uses monolithic extruded molding.
One the most according to claim 1 monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour, it is special
Levy and be that the main component of catalyst is by CuO, ZnO, Al2O3、Cr2O3、CeO2And the composition such as auxiliary agent is constituted；Wherein CuO (
65%)、ZnO(≧8%)、Al2O3(≧8%)。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610651673.2A CN106076353A (en) | 2016-08-11 | 2016-08-11 | A kind of monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour |
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| CN201610651673.2A CN106076353A (en) | 2016-08-11 | 2016-08-11 | A kind of monolithic extruded formed honeycomb shape catalyst for preparing hydrogen by reforming methanol and water vapour |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107433200A (en) * | 2017-06-28 | 2017-12-05 | 广西启明氢能源有限公司 | A kind of hydrous ethanol reformation hydrogen production solid catalyst |
| CN108786823A (en) * | 2018-04-25 | 2018-11-13 | 广西民族师范学院 | A kind of preparation and application of bar shaped preparing hydrogen by reforming methanol catalyst |
| CN111153386A (en) * | 2020-01-07 | 2020-05-15 | 浙江大学 | Methanol reforming hydrogen production reactor with silicon carbide ceramic with honeycomb structure |
-
2016
- 2016-08-11 CN CN201610651673.2A patent/CN106076353A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107433200A (en) * | 2017-06-28 | 2017-12-05 | 广西启明氢能源有限公司 | A kind of hydrous ethanol reformation hydrogen production solid catalyst |
| CN108786823A (en) * | 2018-04-25 | 2018-11-13 | 广西民族师范学院 | A kind of preparation and application of bar shaped preparing hydrogen by reforming methanol catalyst |
| CN108786823B (en) * | 2018-04-25 | 2021-02-05 | 广西民族师范学院 | Preparation and application of strip-shaped catalyst for hydrogen production by methanol reforming |
| CN111153386A (en) * | 2020-01-07 | 2020-05-15 | 浙江大学 | Methanol reforming hydrogen production reactor with silicon carbide ceramic with honeycomb structure |
| CN111153386B (en) * | 2020-01-07 | 2021-07-16 | 浙江大学 | Methanol reforming hydrogen production reactor with silicon carbide ceramic with honeycomb structure |
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Application publication date: 20161109 |