CN109908897A - The preparation method of ferroso-ferric oxide supported copper water-gas shift reaction catalyst - Google Patents
The preparation method of ferroso-ferric oxide supported copper water-gas shift reaction catalyst Download PDFInfo
- Publication number
- CN109908897A CN109908897A CN201910249333.0A CN201910249333A CN109908897A CN 109908897 A CN109908897 A CN 109908897A CN 201910249333 A CN201910249333 A CN 201910249333A CN 109908897 A CN109908897 A CN 109908897A
- Authority
- CN
- China
- Prior art keywords
- water
- gas shift
- shift reaction
- reaction catalyst
- catalyst
- 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.)
- Pending
Links
Abstract
The invention discloses a kind of Cu/Fe3O4Water-gas shift reaction catalyst and preparation method thereof.Using sol-gel method, make Cu by adding nonionic emulsifier2+With Fe3+Uniformly mixing on a molecular scale；CuFe is made through gelation, drying and high-temperature roasting in mixed solution2O4Presoma, then Cu/Fe is obtained through reduction3O4Catalyst.Compared with prior art, the present invention cubic phase CuFe more stable using sol-gel method and the obtained structure of high-temperature heat treatment process and chemical property2O4, using it as the Cu/Fe of precursor preparation3O4Catalyst has higher water gas shift reaction activity and stability.
Description
Technical field
The invention belongs to catalyst for preparing hydrogen preparation fields, and in particular to a kind of Cu/Fe3O4Water-gas shift reaction catalyst
Preparation method.
Background technique
A kind of energy carrier of the Hydrogen Energy as clean and effective, is increasingly becoming the important component of various countries' energy system.Water
Gas shift reaction is the significant process for producing Hydrogen Energy, and the process is using chemical fuel or biomass material is reformed or gasification product
In CO by H2H in O is converted into H2, while reducing CO concentration and obtaining clean hydrogen.
The water gas converting catalyst of existing industrial application mainly has Cu system low temperature conversion catalyst, uses temperature 180-
260 ℃；Fe-Cr system high temperature conversion catalyst, uses temperature > 280 DEG C；The wide warm sulfur-resistant transformation catalyst of Co-Mo system.To improve
The use temperature of Cu series catalysts, often through synthesis CuM2O4The composite oxides of spinel structure, are aoxidized using spinel-type
The chemical property and structural stability of object obtain the small and stable Cu base catalyst of Cu particle size.With inverse spinel structure
CuFe2O4It is considered as one of good presoma of Cu base catalyst, the Cu and Fe of nano-scale can be obtained after reduction3O4, compared with
Preferable water gas shift reaction activity is shown in wide reaction warm area.
Xing Zheng etc. uses solid state reaction, and controls roasting condition, and cubic phase (400 DEG C of roastings) and four directions is made
Phase CuFe2O4(800 DEG C of roastings).But solid state reaction is extended influence seriously, and copper and iron cannot be made uniformly to mix on a molecular scale
It closes, the interaction between copper and iron is weaker.Sol-gel method can be such that raw material uniformly mixes on a molecular scale, but the method is closed
At CuFe2O4It is in tetragonal phase, cubic phase CuFe after high-temperature roasting2O4It can only be stabilized under the conditions of Low Temperature Heat Treatment.It is vertical
Side's phase and tetragonal phase CuFe2O4In ion distribution it is different, there are larger differences for chemical stability.Therefore, as can developing one kind
By CuFe2O4High-temperature heat treatment is carried out, the preparation method of cube phase structure is still kept, to raising Cu/Fe3O4The water coal of catalyst
Gas conversion reaction activity and stability are of great significance.
Summary of the invention
It is an object of the invention to overcome the stability of Cu base catalyst difference and using the low technical problem of temperature, provide from
And a kind of high-performance ferroso-ferric oxide supported copper water-gas shift reaction catalyst and preparation method thereof.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of Cu/Fe3O4Water-gas shift reaction catalyst, preparing raw material includes mantoquita, molysite and emulsifier, preparation method packet
Include following steps:
(1) any two kinds of components in certain proportion in mantoquita, molysite and emulsifier are mixed, is scattered in deionized water, in 25-60
0.5-4 h is mixed under the conditions of DEG C；The third raw material is added, constant temperature in 50-75 DEG C of oil bath is placed in and continues to stir 0.5-4
H forms colloidal sol；
(2) system temperature is risen to 85-110 DEG C, and adjusts pH value to 3.0-6.0, continued to stir 1-5 h, form gel；
(3) gel in step (2) is fired to form CuFe after 140-170 DEG C of dry 3-8 h2O4Presoma；
(4) at a certain temperature, by CuFe2O4Presoma, which restores, is made Cu/Fe3O4Catalyst.
The mantoquita includes that copper nitrate, copper acetate, copper chloride or copper sulphate are one or more of.
The molysite includes that ferric nitrate, iron chloride, frerrous chloride, ferric sulfate or ferrous sulfate are one or more of.
The emulsifier is one of glycol ester, polyvinyl alcohol, glyceride or neopentyl polyol ester.
The molar ratio of the mantoquita and molysite is 1:2.
The dosage of the emulsifier are as follows: emulsifier: [Cu2++Fe3+] atomic ratio be 1-4:1.
Step (3) maturing temperature is 600-900 DEG C, calcining time 1-6 h.
Step (4) reduction temperature is 200-350 DEG C, recovery time 2-4 h.
Remarkable advantage of the invention is:
The present invention makes Cu by selecting suitable nonionic emulsifier2+With Fe3+Uniformly mixing on a molecular scale；It mixes molten
Liquid is handled through gelation, drying and high-temperature roasting, obtains cubic phase CuFe2O4Presoma；Cubic phase CuFe2O4Structure and change
It learns property to stablize, is restored through suitable condition, nano-scale can be formed and stable Cu/Fe3O4Catalyst.Cu of nano-scale
Grain shows good CO adsorption capacity at low temperature；Cu/Fe3O4Catalyst nano also helps Reinforced Cu-Fe3O4Between
Interaction improves it and dissociates outlet capacity and Cu and Fe3O4Stability, to show good wide warm water gas conversion
Reactivity and stability.
Detailed description of the invention
Fig. 1 is the H of presoma prepared by embodiment 1 and comparative example 12- TPR curve.
Fig. 2 is the XRD spectra of embodiment 1, presoma prepared by comparative example 1 and comparative example 2.
Specific embodiment
In order to make content of the present invention easily facilitate the understanding of one skilled in the art, below with reference to specific
Embodiment is described further technical solutions according to the invention.
Embodiment 1
Nine water ferric nitrate of 3.962 g nitrate trihydrate copper and 13.251 g is weighed, is dissolved in 300 mL deionized waters, in 50 DEG C of oil
After 3 h of bath stirring, 25.516 g polyvinyl alcohol are added and continue to stir 2 h under the conditions of 50 DEG C, form gel.By system temperature
Degree rises to 90 DEG C, and adjusts pH value to 4.0, continues to stir 3 h, evaporation water obtains gel.By the gel of acquisition 150
After DEG C dry 4 h, 3 h are roasted in 700 DEG C of still air to get cubic phase CuFe2O4.By the CuFe of acquisition2O4250
Cu/Fe is made in DEG C reductase 12 h3O4Catalyst.
Embodiment 2
3.962 g nitrate trihydrate copper and 8.650 g Iron trichloride hexahydrates are weighed, are dissolved in 350 mL deionized waters, in 60 DEG C of oil baths
After stirring 2 h, 5.997 g glycol esters are added and in 70 DEG C of 2.5 h of stirring, formation gel.System temperature is risen to 100
DEG C, and pH value is adjusted to 3.0, continue to stir 4.5 h, evaporation water obtains gel.Gel after 140 DEG C of dry 6 h,
2.5 h are roasted in 750 DEG C of still air to get cubic phase CuFe2O4.By the CuFe of acquisition2O4In 250 DEG C of 4 h of reduction,
Cu/Fe is made3O4Catalyst.
Embodiment 3
Nine water ferric nitrate of 3.194 g, mono- water copper acetate and 13.251 g is weighed, is dissolved in 330 mL deionized waters, in 55 DEG C of oil
After 3.5 h of bath stirring, 42.791 g glyceride are added and in 75 DEG C of 1.5 h of stirring, formation gel.System temperature is risen to 95
DEG C, and pH value is adjusted to 4.0, continue to stir 3.5 h, evaporation water obtains gel.By the gel of acquisition at 170 DEG C dry 4
After h, 5 h are roasted in 600 DEG C of still air to get cubic phase CuFe2O4.By the CuFe of acquisition2O4It is restored at 300 DEG C
Cu/Fe is made in 2.5 h3O4Catalyst.
Embodiment 4
3.194 g, mono- water copper acetate and 8.650 g Iron trichloride hexahydrates are weighed, are dissolved in 280 mL deionized waters.In 40 DEG C of oil baths
After stirring 2.5 h, 46.576 g neopentyl polyol esters are added and in 55 DEG C of 3 h of stirring, formation gel.By system temperature liter
To 105 DEG C, and pH value is adjusted to 4.0, continue to stir 1.5 h, evaporation water obtains gel.Gel is through 165 DEG C of dry 5 h
Afterwards, 4 h are roasted in 800 DEG C of still air to get cubic phase CuFe2O4.By the CuFe of acquisition2O4In 350 DEG C of reductase 12s
Cu/Fe is made in h3O4Catalyst.
Embodiment 5
Nine water ferric nitrate of 3.962 g nitrate trihydrate copper and 13.251 g is weighed, is dissolved in 300 mL deionized waters, in 40 DEG C of oil
After 2.5 h of bath stirring, 25.516 g polyvinyl alcohol are added, and in 70 DEG C of 4 h of stirring, form gel.System temperature is risen to 85
DEG C, and pH value is adjusted to 3.0,4 h water are then evaporated, gel is obtained.By the gel of acquisition after 155 DEG C of dry 5.5 h,
3.5 h are roasted in 550 DEG C of still air to get cubic phase CuFe2O4.By the CuFe of acquisition2O43.5 are restored at 200 DEG C
Cu/Fe is made in h3O4Catalyst.
Embodiment 6
It weighs 3.962 g nitrate trihydrate copper and 5.997 g glycol esters is dissolved in 310 mL deionized waters, stirred in 35 DEG C of oil baths
After mixing 2.5 h, 13.251 g, nine water ferric nitrate is added and in 65 DEG C of 3.5 h of stirring.System temperature is risen to 97 DEG C, and is adjusted
Then pH value evaporates 2.5 h water, obtains gel to 6.0.It is quiet at 650 DEG C by the gel of acquisition after 145 DEG C of dry 7 h
2.5 h are roasted in state air to get cubic phase CuFe2O4.By the CuFe of acquisition2O4In 250 DEG C of reductase 12 .5 h, Cu/ is made
Fe3O4Catalyst.
Embodiment 7
It weighs 13.251 g, nine water ferric nitrate and 42.791 g glyceride is dissolved in 320 mL deionized waters, stirred in 40 DEG C of oil baths
After mixing 4 h, 3.962 g nitrate trihydrate copper are added and in 55 DEG C of 1.5 h of stirring.System temperature is risen to 110 DEG C, and adjusts pH
Then value evaporates 2 h water, obtains gel to 5.0.It is empty in 900 DEG C of static state by the gel of acquisition after 155 DEG C of dry 5 h
1 h is roasted in gas to get cubic phase CuFe2O4.By the CuFe of acquisition2O4In 250 DEG C of 3 h of reduction, Cu/Fe is made3O4Catalysis
Agent.
Comparative example 1
Nine water ferric nitrate of 3.962 g nitrate trihydrate copper and 13.251 g is weighed, is dissolved in 300 mL deionized waters.In 50 DEG C of oil
After 3 h of bath stirring, 4.469 g ethylene glycol (C are added2H6O2) and continue to stir 2 h.System temperature is risen to 90 DEG C, and is adjusted
Then pH value evaporates 3 h water, obtains gel to 4.0.By the gel of acquisition after 150 DEG C of dry 4 h, in 400 DEG C of static state
3 h are roasted in air to get cubic phase CuFe2O4.By the CuFe of acquisition2O4In 300 DEG C of reductase 12 h, Cu/Fe is made3O4Catalysis
The H of presoma prepared by agent, embodiment 1 and comparative example 12- TPR curve is shown in Fig. 1.
Comparative example 2
Nine water ferric nitrate of 3.962 g nitrate trihydrate copper and 13.251 g is weighed, is dissolved in 300 mL deionized waters.In 60 DEG C of oil
After 2 h of bath stirring, 20.914 g polyvinylpyrrolidones are added and continue to stir 2 h.System temperature is increased to 90 DEG C, and
PH value is adjusted to 4.0,3 h water is then evaporated, obtains gel.By the gel of acquisition after 150 DEG C of dry 4 h, at 700 DEG C
3 h are roasted in still air to get tetragonal phase CuFe2O4.The XRD of presoma prepared by embodiment 1, comparative example 1 and comparative example 2
Spectrogram is shown in Fig. 2.
Catalyst performance evaluation
CuFe prepared by embodiment 1-7 and comparative example 1 is measured respectively2O4Each 0.5 mL(40-60 mesh), having internal diameter 12
By CuFe in the fixed bed reactors of mm stainless steel tube2O4In-situ reducing is Cu/Fe3O4.Reduction temperature is 200-350 DEG C, also
Former time 2-4 h, reducing atmosphere are 10 vol.% H2/N2.In 200-400 DEG C of warm area, to Cu/Fe3O4Catalyst carries out water
Gas shift activity evaluation.Mass space velocity is 9000 h-1, unstripped gas group is as 15 vol. % CO, 55 vol. % H2、7
vol. % CO2With 23 vol. % N2, gas to steam ratio 1:1, test result is shown in Table 1.As it can be seen from table 1 prepared by embodiment 1-7
Cu/Fe3O4Catalyst is compared with the cubic phase CuFe that comparative example 1(is prepared with low-temperature bake2O4For presoma) and comparative example 2(with low
The tetragonal phase CuFe of temperature roasting preparation2O4For presoma) Cu/Fe3O4Catalyst Water gas shift/WGS activity is higher.This is embodied
Cubic phase CuFe prepared by the present invention2O4Advantage.
Table 1
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with repair
Decorations, are all covered by the present invention.
Claims (8)
1. a kind of Cu/Fe3O4Water-gas shift reaction catalyst, which is characterized in that preparing raw material includes mantoquita, molysite and emulsification
Agent, preparation method include the following steps:
(1) any two kinds in mantoquita, molysite and emulsifier are mixed in proportion, is scattered in deionized water, at 25-60 DEG C
Under the conditions of be mixed 0.5-4 h；The third raw material is added, constant temperature in 50-75 DEG C of oil bath is placed in and continues to stir 0.5-4 h,
Form colloidal sol；
(2) system temperature is risen to 85-110 DEG C, and adjusts pH value to 3.0-6.0, continued to stir 1-5 h, form gel；
(3) gel in step (2) is fired to form CuFe after 140-170 DEG C of dry 3-8 h2O4Presoma；
(4) at a certain temperature, by CuFe2O4Presoma, which restores, is made Cu/Fe3O4Catalyst.
2. a kind of Cu/Fe according to claim 13O4Water-gas shift reaction catalyst, which is characterized in that the mantoquita
It is one or more of including copper nitrate, copper acetate, copper chloride or copper sulphate.
3. a kind of Cu/Fe according to claim 13O4Water-gas shift reaction catalyst, which is characterized in that the molysite
It is one or more of including ferric nitrate, iron chloride, frerrous chloride, ferric sulfate or ferrous sulfate.
4. a kind of Cu/Fe according to claim 13O4Water-gas shift reaction catalyst, which is characterized in that the emulsification
Agent is one of glycol ester, polyvinyl alcohol, glyceride or neopentyl polyol ester.
5. a kind of Cu/Fe according to claim 13O4Water-gas shift reaction catalyst, which is characterized in that the mantoquita
Molar ratio with molysite is 1:2.
6. a kind of Cu/Fe according to claim 13O4Water-gas shift reaction catalyst, which is characterized in that the emulsification
The dosage of agent are as follows: emulsifier: [Cu2++Fe3+] atomic ratio be 1-4:1.
7. a kind of Cu/Fe according to claim 13O4Water-gas shift reaction catalyst, which is characterized in that step (3) institute
Stating maturing temperature is 600-900 DEG C, calcining time 1-6 h.
8. a kind of Cu/Fe according to claim 13O4Water-gas shift reaction catalyst, which is characterized in that step (4) institute
Stating reduction temperature is 200-350 DEG C, recovery time 2-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910249333.0A CN109908897A (en) | 2019-03-29 | 2019-03-29 | The preparation method of ferroso-ferric oxide supported copper water-gas shift reaction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910249333.0A CN109908897A (en) | 2019-03-29 | 2019-03-29 | The preparation method of ferroso-ferric oxide supported copper water-gas shift reaction catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109908897A true CN109908897A (en) | 2019-06-21 |
Family
ID=66967482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910249333.0A Pending CN109908897A (en) | 2019-03-29 | 2019-03-29 | The preparation method of ferroso-ferric oxide supported copper water-gas shift reaction catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109908897A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105381780A (en) * | 2015-12-07 | 2016-03-09 | 中国科学院生态环境研究中心 | Magnetic absorbent for removing arsenic and antimony through adsorption-superconducting magnetic separating and preparation method thereof |
| US20160311682A1 (en) * | 2014-10-24 | 2016-10-27 | Research Triangle Institute | Systems and methods for water gas shift with reduced steam consumption |
| CN107754815A (en) * | 2017-10-30 | 2018-03-06 | 福州大学 | A kind of renovation process of copper/ferroferric oxide water gas converting catalyst |
-
2019
- 2019-03-29 CN CN201910249333.0A patent/CN109908897A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160311682A1 (en) * | 2014-10-24 | 2016-10-27 | Research Triangle Institute | Systems and methods for water gas shift with reduced steam consumption |
| CN105381780A (en) * | 2015-12-07 | 2016-03-09 | 中国科学院生态环境研究中心 | Magnetic absorbent for removing arsenic and antimony through adsorption-superconducting magnetic separating and preparation method thereof |
| CN107754815A (en) * | 2017-10-30 | 2018-03-06 | 福州大学 | A kind of renovation process of copper/ferroferric oxide water gas converting catalyst |
Non-Patent Citations (2)
| Title |
|---|
| CHEN CHONGQI ET AL.: "Cu/Fe3O4 catalyst for water gas shift reaction:Insight into the effect of Fe2þ and Fe3þ distribution in Fe3O4", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| LIN XINGYI ET AL.: "The role of surface copper species in Cu-Fe composite oxide catalysts for the water gas shift reaction", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112958137B (en) | Method for treating waste gas by using cobaltosic oxide dodecahedron/carbon nitride nano-sheet compound | |
| CN104707636B (en) | Pt/α‑MoC1‑xLoaded catalyst and its synthesis and application | |
| CN113289693B (en) | Ammonia decomposition catalyst and preparation method and application thereof | |
| CN110280290B (en) | Flower-shaped nitrogen-doped carbon-spinel microsphere catalyst with high specific surface area and preparation method and application thereof | |
| US9499402B2 (en) | Method for preparing a supported ruthenium catalyst | |
| Da et al. | Catalytic oxidation of diesel soot particulates over Pt substituted LaMn1-xPtxO3 perovskite oxides | |
| CN110876938A (en) | Perovskite type composite metal oxide oxygen carrier and preparation method and application thereof | |
| Zeng et al. | Nanostructured Fe2O3/MgAl2O4 material prepared by colloidal crystal templated sol–gel method for chemical looping with hydrogen storage | |
| CN104971727B (en) | A kind of preparation method of Ni-based catalyst for hydrogen production from methane vapor reforming | |
| CN108517537A (en) | Double scale transition metal phosphides of a kind of nitrogen-doped carbon load and its preparation method and application | |
| CN109759070B (en) | Perovskite type titanium strontium Co catalysts for acetic acid self-heating reforming hydrogen manufacturing | |
| CN107597119B (en) | Carbon deposition resistant cobalt-based low-temperature methane carbon dioxide reforming catalyst and preparation method thereof | |
| CN109569607A (en) | A kind of preparation method of novel cobalt-based composite material | |
| CN112058270A (en) | Flaky La0.8Sr0.2CoO3In-situ synthesis method and application of perovskite catalyst | |
| CN105618081A (en) | Rare earth metal La doped copper manganese catalyst and experiment method thereof | |
| CN101982418A (en) | Preparation method of perovskite LnCrO3 and LnAlO3 nanomaterials | |
| Wang et al. | Preparation, characterization and catalytic performance of ordered macroporous-mesoporous SiO2-supported MnMOx catalysts for soot combustion | |
| JP2010029822A (en) | Steam reforming catalyst | |
| CN103272630A (en) | Nickel-based catalyst taking yttrium-doped SBA-15 as carrier, and preparation method and application thereof | |
| CN113122878A (en) | Nitrogen-doped carbon composite graphene coated metal cobalt catalyst, preparation method and application | |
| Neha et al. | Facile and template-free synthesis of nano-macroporous LaCoO3 perovskite oxide for efficient diesel soot oxidation | |
| Xu et al. | Promotional effects of Sm/Ce/La doping on soot oxidation over MnCo2O4 spinel catalysts | |
| CN116078419B (en) | Carbon nitride of cobalt phosphide coated by core-shell amorphous cobalt phosphate | |
| Huang et al. | Hierarchically porous calcium-based composites synthesized by eggshell membrane templating for thermochemical energy storage of concentrated solar power | |
| CN109908897A (en) | The preparation method of ferroso-ferric oxide supported copper water-gas shift reaction catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190621 |