CN109759105A - A kind of methanol synthesis catalyst - Google Patents
A kind of methanol synthesis catalyst Download PDFInfo
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- CN109759105A CN109759105A CN201910175496.9A CN201910175496A CN109759105A CN 109759105 A CN109759105 A CN 109759105A CN 201910175496 A CN201910175496 A CN 201910175496A CN 109759105 A CN109759105 A CN 109759105A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention relates to CO/CO under industrial atmosphere2The Cu-series catalyst of synchronous preparing methanol by hydrogenation provides a kind of methanol synthesis catalyst that the active, service life is improved, realizes CO/CO2Synchronous preparing methanol by hydrogenation Efficient Conversion, the catalyst are applied to synthesizing methanol, selectively reach 100%.Catalyst composition of the present invention includes Cu, Mo2C and SiO2, wherein the mass content of Cu is 0~25%, Mo2The mass content of C is 0~25%, SiO2Mass content be 50~75%.Catalyst of the present invention, without reduction, is being convenient for large-scale promotion and application using preceding.
Description
Technical field
The invention belongs to catalyst technical fields, are related to a kind of for methanol synthesis catalyst under cryogenic conditions.Specifically relate to
And CO/CO under industrial atmosphere2The Cu-series catalyst of synchronous preparing methanol by hydrogenation.
Background technique
Methanol is basic chemical industry raw material and potential vehicle fuel and hydrogen donor.Industrial methanol is produced with synthesis gas (CO/
CO2/H2) it is raw material, ICI Imperial Chemical Industries Cu/ZnO/Al is mainly used in fixed bed reactors2O3Catalyst.In the catalyst
In, copper is active component, and zinc is auxiliary agent, and synergistic effect between the two is the key factor that catalyst has high activity, specifically
For, the effect of ZnO is storage overflow hydrogen, promotes the reaction in Cu active sites, and the dispersion degree and Cu-Zn active site density of Cu is determined
The height of catalyst activity is determined；Aluminium oxide plays the role of providing bracket for active material as carrier, when active material is equal
Even ground single layer be attached to the carrier surface of high dispersive i.e. effective rate of utilization maximum when, the activity of catalyst also just reaches highest.On
Activity of the Cu-series catalyst with the synthesis of good catalysis methanol under lower pressure and temperature is stated, and efficiency of carbon con version is high, produces
Impurity content in object is low, thus is widely applied.But since the thermal discharge of methanol synthesis reaction is big, it be easy to cause copper system
The sintering of copper, leads to catalyst inactivation in catalyst, substantially reduces the service life of catalyst.
In recent years, due to considering economy and global warming, the unstrpped gas of methanol-fueled CLC by two sections of modified methods or
Carbon dioxide variation is added as the unstrpped gas composition of rich carbon, the Cu series catalysts of report synthesizing methanol under cryogenic, table
It is not high to reveal selectivity, service life short problem.
Therefore, the thermal stability for how effectively improving Cu-series catalyst for synthesizing methanol, prolongs its service life, it has also become tired
Disturb the research direction of those skilled in the art.
Summary of the invention
The technical problem to be solved in the present invention is that overcoming thermostabilization present in existing Cu-series catalyst for synthesizing methanol
Property poor, defect that service life is short, and then a kind of copper system methanol-fueled CLC heat-resist, that the service life is long and catalytic activity is high is provided and is urged
Agent.
Beneficial effects of the present invention also reside in catalyst and may be directly applied to synthesizing methanol by hydrogenating without reduction using preceding,
To reduce reaction process, economic benefit is improved.
The present invention conducts in-depth research intending to solve the above problem, has carried out serial experiment, and obtaining can be with
Improve activity, the service life, intensity methanol synthesis catalyst most suitable composition and its preparation condition, so as to complete the present invention.
Catalyst of the invention contains Cu, Mo2C and SiO2, wherein the mass content of Cu is 0~25 %, Mo2The quality of C contains
Amount is 0~25 %, SiO2Mass content be 50~75 %；Catalyst is aperture in 2.5 ~ 8 nm, and specific surface area is 100 ~ 180
m2/g； Mo2C is β-Mo2C；β-Mo2C high preferred orientation is 100,002,101,102,110,103,200；Cu high preferred orientation is
111,200,220；SiO2For unformed state；Cu is 0 valence state or+1 valence state.The dispersion degree of catalyst Cu is 80% or more.And
And catalyst can also mix Zn, Al, K, Mg, Fe element.
The present invention utilizes the mesoporous Cu/Mo of carbonizatin method preparation2C/SiO2Catalyst, wherein Cu and Mo2C is activated centre,
SiO2For carrier.Increase surface area and activated centre dispersion degree；Promote raw molecule CO and CO2Absorption, activation, reach catalysis
The purpose of reaction.
Catalyst of the present invention contains Cu, Mo2C and SiO2, the mass content of Cu is 0~25 %, Mo in catalyst2The quality of C
Content is 0~25 %, SiO2Mass content be 50~75 %.Copper, molybdenum, carbon, silicon and oxygen are respectively derived from copper nitrate, ammonium molybdate
And polymethyl hydrogen siloxane.Ethylenediamine is wherein added in presoma forming process plays facilitation.
The preparation method of catalyst of the present invention the following steps are included:
(1) the desired amount of ammonium molybdate is weighed, ethyl alcohol is dissolved in, stirs 24 h, suspending liquid A is made；
(2) the desired amount of Copper nitrate hexahydrate is weighed, is added in suspending liquid A, suspension B is made in 1 h of stirring；
(3) the desired amount of polymethyl hydrogen siloxane is weighed, is 4~7 and ethylenediamine by C:Mo molar ratio, is added in suspension B, stirs
It mixes 12 h and suspension C is made；
(4) 60~80 °C of dry suspension C；Presoma is made in 150 °C of 10 h of drying；
(5) presoma is weighed, in nitrogen atmosphere, catalyst is made in 500~900 °C of 2~6 h of calcination process；
(6) by the one or more of infusion process addition Zn, Al, K, Mg, Fe element.
It is made it is noted that the calcination process of step (5) is temperature-gradient method processing, from room temperature with the rate liter of 5 °C/min
Temperature is warming up to 700 °C to 350 °C, then with the rate of 5 °C/min, and be carbonized 3 h, wherein N2Flow velocity is 50 ~ 150 mL/min；
It is characterized in that roasting generates methane reduction gas, metallic element is reduced.Especially metallic copper Cu valence state is reduced to 0 valence state
Or+1 valence state.
The determination of activity step of catalyst of the present invention: carrying out in semicontinuous flowing paste state bed reactor, unstripped gas composition
For the % of CO(25~35), CO2(0~10 %) and H2(55~65 %), flow velocity are 20 mL/min, and 40 mL ethyl alcohol of solvent medium is urged
4 g of agent, 90~150 °C of reaction temperature, 3~5 MPa of reaction pressure, 850 r. p.m of mixing speed, the online reaction time 20
h。
Detailed description of the invention
Fig. 1 is the object phasor of 3 catalyst sample of embodiment.
Specific embodiment
Embodiment 1
Weigh 2.9 g (NH4)6Mo7O24∙4H2O grinds 10 min, is dissolved in 150 mL ethyl alcohol, stirs 24 h；1.5 g Cu are added
(NO3)2∙3H2O stirs 1 h；5.8 g C are slowly added dropwise3H9OSi∙(CH4OSi)n∙C3H9The drop ethylenediamine of Si and 2, stirs 12 h；80
°C dry 6 h；150 °C of 10 h of drying；Catalyst is made in 700 °C of nitrogen atmosphere 3 h of processing.Wherein the mass content of Cu is 5
%, Mo2The mass content of C is 21 %, SiO2Mass content be 74 %.The hole size of sample is 3.9 nm, pore volume 120
mm3/ g, surface area are 117.3 m2/g.Methanol-fueled CLC activity rating: unstripped gas forms CO 31.2 %, CO2 5.0 %、H2
61.8 %.Reaction temperature is 150 °C, and 4 MPa of reaction pressure the results are shown in Table 1.
Embodiment 2
Weigh 2.9 g (NH4)6Mo7O24∙4H2O grinds 10 min, is dissolved in 150 mL ethyl alcohol, stirs 24 h；3.1 g Cu are added
(NO3)2∙3H2O stirs 1 h；5.8 g C are slowly added dropwise3H9OSi∙(CH4OSi)n∙C3H9The drop ethylenediamine of Si and 2, stirs 12 h；80
°C dry 6 h；150 °C of 10 h of drying；Catalyst is made in 700 °C of nitrogen atmosphere 3 h of processing.Wherein the mass content of Cu is
10 %, Mo2The mass content of C is 20 %, SiO2Mass content be 70 %.The hole size of sample is 4.1 nm, and pore volume is
150 mm3/ g, surface area are 151.4 m2/g.Methanol-fueled CLC activity rating the results are shown in Table 1 referring to embodiment 1.
Embodiment 3
Weigh 2.9 g (NH4)6Mo7O24∙4H2O grinds 10 min, is dissolved in 150 mL ethyl alcohol, stirs 24 h；4.9 g Cu are added
(NO3)2∙3H2O stirs 1 h；5.8 g C are slowly added dropwise3H9OSi∙(CH4OSi)n∙C3H9The drop ethylenediamine of Si and 2, stirs 12 h；80
°C dry 6 h；150 °C of 10 h of drying；Catalyst is made in 700 °C of nitrogen atmosphere 3 h of processing.Wherein the mass content of Cu is
15 %, Mo2The mass content of C is 19 %, SiO2Mass content be 66 %.The hole size of sample is 4.3 nm, and pore volume is
170 mm3/ g, surface area are 154.3 m2/g.Methanol-fueled CLC activity rating the results are shown in Table 1 referring to embodiment 1.
Embodiment 4
Weigh 2.9 g (NH4)6Mo7O24∙4H2O grinds 10 min, is dissolved in 150 mL ethyl alcohol, stirs 24 h；7.0 g Cu are added
(NO3)2∙3H2O stirs 1 h；5.8 g C are slowly added dropwise3H9OSi∙(CH4OSi)n∙C3H9The drop ethylenediamine of Si and 2, stirs 12 h；80
°C dry 6 h；150 °C of 10 h of drying；Catalyst is made in 700 °C of nitrogen atmosphere 3 h of processing.Wherein the mass content of Cu is
20 %, Mo2The mass content of C is 18 %, SiO2Mass content be 62 %.The hole size of sample is 4.6 nm, and pore volume is
184 mm3/ g, surface area are 159.3 m2/g.Methanol-fueled CLC activity rating the results are shown in Table 1 referring to embodiment 1.
Embodiment 5
Catalyst preparation is referring to embodiment 3.
Methanol-fueled CLC activity rating: referring to embodiment 1, reaction temperature is 130 °C, the results are shown in Table 1.
Embodiment 6
Catalyst preparation is referring to embodiment 3.
Methanol-fueled CLC activity rating: referring to embodiment 1, reaction temperature is 110 °C, the results are shown in Table 1.
Embodiment 7
Catalyst preparation is referring to embodiment 3.
Methanol-fueled CLC activity rating: referring to embodiment 1, reaction temperature is 90 °C, the results are shown in Table 1.
Fig. 1 shows the catalyst of preparation in 2 θ=34.4o, 37.9o, 39.4o, 52.1o, 61.5o, 69.6o and 74.6o
Diffraction maximum be attributed to β-Mo2(100), (002), (101), (102), (110), (103) and (200) crystal face of C, 2 θ=
The diffraction maximum of 43.4o, 50.6o and 74.2o are attributed to (111), (200) and (220) crystal face of Cu, do not occur silicon dioxide features
Diffraction maximum shows that silica is unformed state.
Table 1 is the methanol-fueled CLC activity list of catalyst.
Table 1 is the methanol-fueled CLC activity of catalyst.With increasing for copper additional amount, activity first improves to be declined afterwards, when copper is added
Catalyst activity highest when amount is 15 %.Catalyst activity height has benefited from that specific surface area is larger, and no ordered meso-porous structure is more, catalysis
Agent crystal grain is smaller, and aperture is moderate, while stronger to the adsorption activation of unstripped gas；Increasing for copper additional amount increases catalytic active site
Point, but copper excessively will lead to copper particle diameter excessive, easy-sintering, drop afterwards so first improving with the raising catalytic activity of copper additional amount
It is low.For catalyst prepared by embodiment 3, the conversion that evaluation temperature is conducive to raw material is reduced, is reduced with evaluation temperature, is catalyzed
Agent activity first increases to be reduced afterwards, the activity highest when temperature is 110 oC.Utilize N2O-Oxidation measures embodiment 3 and is catalyzed
The dispersion degree of Cu is 85.0 % in agent, shows that catalyst degree of scatter is preferable.
Claims (5)
1. a kind of methanol synthesis catalyst, it is characterised in that: the catalyst contains Cu, Mo2C and SiO2, wherein Cu and Mo2C is
Activated centre, SiO2For carrier；It is characterized in that the mass content of Cu is 0~25 %, Mo2The mass content of C is 0~25 %,
SiO2Mass content be 50~75 %；The catalyst is aperture in 2.5 ~ 8nm, and specific surface area is 100 ~ 180 m2/g；It is special
Sign is the Mo2C is β-Mo2C；β-the Mo2C high preferred orientation is 100,002,101,102,110,103,200；Cu crystal face
It is oriented to 111,200,220；The SiO2For unformed state；The Cu is 0 valence state or+1 valence state.
2. a kind of methanol synthesis catalyst according to claim 1, it is characterised in that the dispersion degree of the catalyst Cu exists
80% or more.
3. a kind of methanol synthesis catalyst according to claim 1, it is characterised in that the catalyst can also mix Zn,
Al, K, Mg, Fe element.
4. a kind of methanol synthesis catalyst according to claim 1, it is characterised in that the preparation method of catalyst include with
Lower step:
(1) the desired amount of ammonium molybdate is weighed, ethyl alcohol is dissolved in, stirs 24 h, suspending liquid A is made；
(2) the desired amount of Copper nitrate hexahydrate is weighed, is added in suspending liquid A, suspension B is made in 1 h of stirring；
(3) the desired amount of polymethyl hydrogen siloxane is weighed, is 4~7 and ethylenediamine by C:Mo molar ratio, is added in suspension B, stirs
It mixes 12 h and suspension C is made；
(4) 60~80 °C of dry suspension C；Presoma is made in 150 °C of 10 h of drying；
(5) presoma is weighed, in nitrogen atmosphere, catalyst is made in 500~900 °C of 2~6 h of calcination process；
(6) by the one or more of infusion process addition Zn, Al, K, Mg, Fe element.
5. a kind of methanol synthesis catalyst according to claim 4, it is characterised in that the calcination process of the step (5) is
Temperature-gradient method processing, is warming up to 350 °C from room temperature with the rate of 5 °C/min, then be warming up to 700 ° with the rate of 5 °C/min
C, be carbonized 3 h, wherein N2Flow velocity is 50 ~ 150 mL/min；It is characterized in that roasting generates methane reduction gas, metal member
Element is reduced.
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| CN201910175496.9A CN109759105B (en) | 2019-03-08 | 2019-03-08 | Methanol synthesis catalyst |
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| CN201910175496.9A CN109759105B (en) | 2019-03-08 | 2019-03-08 | Methanol synthesis catalyst |
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Citations (8)
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| US6677270B2 (en) * | 1999-10-18 | 2004-01-13 | Conocophillips Company | Metal carbide catalysts and process for producing synthesis gas |
| CN101306369A (en) * | 2008-07-11 | 2008-11-19 | 西南化工研究设计院 | Catalyst for synthesizing methanol and preparing process thereof |
| CN101384363A (en) * | 2006-02-17 | 2009-03-11 | 新日铁工程技术株式会社 | Methanol synthesis catalyst, method for producing such catalyst and method for producing methanol |
| CN101384362A (en) * | 2006-02-17 | 2009-03-11 | 新日铁工程技术株式会社 | Methanol synthesis catalyst, method for producing such catalyst and method for producing methanol |
| CN102203034A (en) * | 2008-08-27 | 2011-09-28 | 维仁特能源系统公司 | Synthesis of liquid fuels from biomass |
| CN102958882A (en) * | 2011-04-04 | 2013-03-06 | 国际人造丝公司 | Ethanol production from acetic acid utilizing a molybdenum carbide catalyst |
| CN101679874B (en) * | 2007-03-08 | 2013-10-23 | 维仁特公司 | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
| CN104437467A (en) * | 2014-10-27 | 2015-03-25 | 杭州聚力氢能科技有限公司 | Hydrogenation catalyst, application of hydrogenation catalyst, dehydrogenation catalyst and application of dehydrogenation catalyst |
-
2019
- 2019-03-08 CN CN201910175496.9A patent/CN109759105B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6677270B2 (en) * | 1999-10-18 | 2004-01-13 | Conocophillips Company | Metal carbide catalysts and process for producing synthesis gas |
| CN101384363A (en) * | 2006-02-17 | 2009-03-11 | 新日铁工程技术株式会社 | Methanol synthesis catalyst, method for producing such catalyst and method for producing methanol |
| CN101384362A (en) * | 2006-02-17 | 2009-03-11 | 新日铁工程技术株式会社 | Methanol synthesis catalyst, method for producing such catalyst and method for producing methanol |
| CN101679874B (en) * | 2007-03-08 | 2013-10-23 | 维仁特公司 | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
| CN101306369A (en) * | 2008-07-11 | 2008-11-19 | 西南化工研究设计院 | Catalyst for synthesizing methanol and preparing process thereof |
| CN102203034A (en) * | 2008-08-27 | 2011-09-28 | 维仁特能源系统公司 | Synthesis of liquid fuels from biomass |
| CN102958882A (en) * | 2011-04-04 | 2013-03-06 | 国际人造丝公司 | Ethanol production from acetic acid utilizing a molybdenum carbide catalyst |
| CN104437467A (en) * | 2014-10-27 | 2015-03-25 | 杭州聚力氢能科技有限公司 | Hydrogenation catalyst, application of hydrogenation catalyst, dehydrogenation catalyst and application of dehydrogenation catalyst |
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