CN105214583A - A kind of microreactor for the reaction of methyl alcohol anaerobic dehydrogenation and Synthesis and applications thereof - Google Patents
A kind of microreactor for the reaction of methyl alcohol anaerobic dehydrogenation and Synthesis and applications thereof Download PDFInfo
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- CN105214583A CN105214583A CN201410281063.9A CN201410281063A CN105214583A CN 105214583 A CN105214583 A CN 105214583A CN 201410281063 A CN201410281063 A CN 201410281063A CN 105214583 A CN105214583 A CN 105214583A
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Abstract
The present invention relates to a kind of preparation and application thereof of the capillary microreactor for the reaction of methyl alcohol anaerobic dehydrogenation.Microreactor is built by modifying the oxide carried type noble metal catalyst of one deck in quartz capillary.This capillary microreactor be applied to methyl alcohol anaerobic dehydrogenation research, reach higher methanol conversion under mild conditions and anhydrous formaldehyde selective.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparation and application thereof of the microreactor for the reaction of methyl alcohol anaerobic dehydrogenation.
Background technology
Formaldehyde is a kind of important organic basic industrial chemicals, and in macromolecular material, fine chemistry industry, organic synthesis, medicine intermediate synthesis, fine perfumery synthesis, dyestuff etc., have special applications, economic benefit is very remarkable.Along with the rise of the engineering plastics of synthesized high-performance, PARA FORMALDEHYDE PRILLS(91,95) demand is increasing, and PARA FORMALDEHYDE PRILLS(91,95) concentration requirement is day by day harsh.The existence of water have impact on the exploitation of formaldehyde downstream product.When Lauxite, the phenolic resins of synthesized high-performance, concentration of formaldehyde directly has influence on rate of polymerization and the degree of polymerization, affects the performance of product.And industrial formaldehyde is mainly produced by methanol air oxidizing process, formaldehyde water content is up to more than 50%.The production of anhydrous formaldehyde generally adopts rare aldehyde concentration technology and solvent azeotropic dehydration concentration technology, and because the vapour pressure of formalin is very low, easily form azeotropic system, dehydration separating effect is not good, and energy consumption is large, and isolation andpurification anhydrous formaldehyde is very difficult and expensive.On the other hand, in methanol air oxidizing process, the oxidizable formic acid of formaldehyde, etching apparatus.Therefore, in the urgent need to studying new process, directly produce anhydrous formaldehyde to meet the needs in market by methyl alcohol.
Methyl alcohol direct dehydrogenation is a kind of effective ways preparing anhydrous formaldehyde.The series of problems such as the stability of formalin and purification are all easy to solve.At present, more catalyst mainly a series of metal oxide, slaine, molecular sieve and metal is studied.The research of metal oxide catalyst mainly concentrates on CuO/SiO
2and ZnO/SiO
2.Result of study shows, these catalyst all have good activity and selectivity, wherein ZnO/SiO
2catalyst activity is higher, but stability is generally poor.Weisgickl etc. are with Na
0.5li
0.5alO
2for catalyst, can obtain 98% methanol conversion and 75% formaldehyde selective, but its reaction temperature will up to 900 DEG C, and require harsher to reactor, energy consumption is high, uneconomical.Matsumura etc. are with the ZSM-5 molecular sieve of dealuminzation for catalyst, and formaldehyde yield is 22%.Fudan University Dai Weilin and Fan Kangnian etc. have studied loaded Ag catalyst, has good effect in methanol dehydrogenation.Research finds Ag
+be activated centre, in course of reaction, be easily reduced into metallic state and inactivation.
At present, conventional fixed bed reactor, shaping of catalyst is filled, and shaped granule inside can not be contacted by substrate molecule, and catalytic active center can not expose completely, is also easy to broken, efflorescence in inverse process, blocking reactor.In methanol dehydrogenation process, there is multiple possible competitive reaction process, aldehyde products also can generate CO, H by overreaction further
2, CH
4deng accessory substance.Therefore, except being regulated and controled by Catalyst Design, control the time of staying and mass transport process, reducing the decomposition of aldehyde products, is improve optionally effective ways.Microreactor have mass-and heat-transfer fast, mix, the feature such as high-specific surface area, receive and pay close attention to widely and apply.In the microchannel of confinement, molecular diffusion mass transfer is different from traditional reactor, directly affects elementary reaction process, and the time of staying is also easy to control.Therefore, by depositing one deck catalyst at capillary tube inner wall, preparing capillary microreactor, controlling mass transport process and the time of staying, be expected to improve methanol dehydrogenation changing effect and formaldehyde selective.
Summary of the invention
Object of the present invention provide a kind of for methyl alcohol anaerobic dehydrogenation reaction capillary microreactor and preparation method thereof with application, under capillary microreactor effect, under anaerobic, cryogenic conditions, methyl alcohol direct dehydrogenation, high selectivity obtains anhydrous formaldehyde.
At present, conventional fixed bed reactor, shaping of catalyst is filled, and shaped granule inside can not be contacted by substrate molecule, and catalytic active center can not expose completely, is also easy to broken, efflorescence in inverse process, blocking reactor.In methanol dehydrogenation process, there is multiple possible competitive reaction process, aldehyde products also can be reacted further and be generated CO, H
2, CH
4deng accessory substance.The present invention adopts capillary microreactor to control the time of staying and mass transport process, reduces the decomposition of aldehyde products.In the microchannel of confinement, molecular diffusion mass transfer is different from traditional reactor, directly affects elementary reaction process, and the time of staying is also easy to control.
Oxide carrier in described oxide carried type noble metal catalyst is MgO, CeO
2, ZnO, La
2o
3, one or more in CuO.Described noble metal is one or more of metal in Au, Pd, Pt, Ru, Ag, and the load capacity of noble metal is 0.2-15wt%, preferred 0.5%-5.0wt%.
Described quartz capillary nozzle diameter is 0.5-5mm.
Described oxide carried type noble metal catalyst layer thickness 0.02-0.2mm.
Capillary microreactor preparation can be performed as follows:
(a) capillary tube inner wall amination process
At 300-800 DEG C of temperature, ammonia is passed through quartz capillary with 5-50mL/min flow velocity, process 1-24h.Preferred 500-800 DEG C, 10-30mL/min, 6-12h.
(b) carrier metal ion and precious metal ion eutectoid content
A certain proportion of carrier metal ion and precious metal ion solution are by constant-flux pump by the quartz capillary after amination process, and carrier metal ion and precious metal ion are adsorbed on capillary tube inner wall by quartz capillary inwall amino.The load capacity of noble metal is regulated and controled by the ratio controlling carrier metal ion and precious metal ion.
Carrier metal ion and precious metal ion solution are one in the nitrate of metal, sulfate, chlorate, acetate or two or more; Concentration 0.1-5mol/L; Preferred 0.5-1mol/L.
The flow velocity flowing through quartz capillary is 0.1-5mL/min, and the time is 1-48h.
(c) high-temperature process
Under air, 200-600 DEG C, processes 1-12h to quartz capillary after step (b) being processed.The noble metal catalyst obtaining Metal Supported is deposited on capillary tube inner wall, obtains capillary microreactor.Preferred 300-500 DEG C, 3-6h.
Methanol dehydrogenation reaction is as follows: employing quartz capillary is microreactor, and product adopts on-line measuring device.First use argon gas purge, the air that removing inside retains and impurity, carry out preheating under argon shield; Wherein methyl alcohol volume content is 10%-60%; Reaction temperature is 100-400 DEG C; Flow rate of carrier gas is 5-80mLmin
-1.Particular methanol volume content is 35%-55%; Reaction temperature is 200-300 DEG C; The mass space velocity of bed is 5-100mLg
-1 cats
-1, preferred 20-55mLg
-1 cats
-1.
Catalyst tool provided by the invention has the following advantages: the catalytic activity of catalyst is high, (is less than 400 DEG C) at relatively low temperature and reaches high conversion ratio and selective.
Detailed description of the invention
Embodiment 1
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 500 DEG C, with the flow velocity of 30mL/min, by ammonia by quartz capillary, keep 6h.Be cerous nitrate and the aqueous solution of chloraurate of 1mmol/L by total concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 0.5mL/min, keep 1h.Cerium is 10:1 with the mol ratio of gold.By the capillary after absorption, in air atmosphere, at 400 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 10wt%-Au/CeO
2-MR.
Embodiment 2
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 800 DEG C, with the flow velocity of 5mL/min, by ammonia by quartz capillary, keep 6h.Be cerous nitrate and the chloroplatinic acid aqueous solution of 1mmol/L by total concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 0.5mL/min, keep 1h.The mol ratio of cerium and platinum is 20:1.By the capillary after absorption, in air atmosphere, at 500 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 5.2wt%-Pt/CeO
2-MR.
Embodiment 3
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 400 DEG C, with the flow velocity of 5mL/min, by ammonia by quartz capillary, keep 24h.Be cerous nitrate and the palladium chloride aqueous solution of 1mmol/L by concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 0.5mL/min, keep 1h.The mol ratio of cerium and palladium is 20:1.By the capillary after absorption, in air atmosphere, at 300 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 4.5wt%-Pd/CeO
2-MR.
Embodiment 4
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 500 DEG C, with the flow velocity of 20mL/min, by ammonia by quartz capillary, keep 12h.Be cerous nitrate and the ruthenium trichloride aqueous solution of 1mmol/L by concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 0.5mL/min, keep 1h.The mol ratio of cerium and ruthenium is 20:1.By the capillary after absorption, in air atmosphere, at 600 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 3.1wt%-Ru/CeO
2-MR.
Embodiment 5
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 500 DEG C, with the flow velocity of 20mL/min, by ammonia by quartz capillary, keep 12h.Be cerous nitrate and the silver nitrate aqueous solution of 1mmol/L by concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 0.5mL/min, keep 1h.Cerium is 20:1 with the mol ratio of silver.By the capillary after absorption, in air atmosphere, at 300 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 1.2wt%-Ag/CeO
2-MR.
Embodiment 6
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 500 DEG C, with the flow velocity of 20mL/min, by ammonia by quartz capillary, keep 12h.Be magnesium nitrate and the aqueous solution of chloraurate of 0.1mmol/L by concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 1mL/min, keep 1h.Magnesium is 20:1 with the mol ratio of gold.By the capillary after absorption, in air atmosphere, at 400 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 5.5wt%-Au/MgO-MR.
Embodiment 7
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 500 DEG C, with the flow velocity of 20mL/min, by ammonia by quartz capillary, keep 12h.Be zinc nitrate and the aqueous solution of chloraurate of 1mmol/L by concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 0.5mL/min, keep 1h.Zinc is 20:1 with the mol ratio of gold.By the capillary after absorption, in air atmosphere, at 400 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 4.5wt%-Au/ZnO-MR.
Embodiment 8
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 500 DEG C, with the flow velocity of 20mL/min, by ammonia by quartz capillary, keep 12h.Be copper nitrate and the aqueous solution of chloraurate of 1mmol/L by concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 0.1mL/min, keep 24h.Copper is 20:1 with the mol ratio of gold.By the capillary after absorption, in air atmosphere, at 400 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 3.5wt%-Au/CuO-MR.
Embodiment 9
Adopt internal diameter be the quartz capillary of 3mm as microreactor, at 500 DEG C, with the flow velocity of 20mL/min, by ammonia by quartz capillary, keep 12h.Be lanthanum nitrate and the aqueous solution of chloraurate of 1mmol/L by concentration, pass through quartz capillary by constant-flux pump with the flow velocity of 2mL/min, keep 1h.Lanthanum is 20:1 with the mol ratio of gold.By the capillary after absorption, in air atmosphere, at 400 DEG C, calcine 3h.Obtain quartz capillary as microreactor, can called after 5.5wt%-Au/La
2o
3-MR.
Embodiment 10-29
Obtained quartz capillary microreactor is used for methyl alcohol direct dehydrogenation to prepare in anhydrous formaldehyde reaction, uses argon gas purge, the air that removing inside retains and impurity, carry out preheating under argon shield; With Ar gas for carrier gas, with certain flow velocity, methanol steam is incorporated in beds.Product adopts online gas chromatographic analysis, the results are shown in Table 1.
Table 1 different catalysts microreactor catalysis methanol anaerobic dehydrogenation result
As can be seen from Table 1, microreactor of the present invention is adopted, with MgO, CeO
2, ZnO, La
2o
3, CuO is carrier, Au, Pd, Pt, Ru, Ag are noble metal component, at a lower temperature, all have the conversion ratio of the selective and higher methyl alcohol of high formaldehyde.
Claims (7)
1. for a microreactor for methyl alcohol anaerobic dehydrogenation reaction, it is characterized in that: modify at quartz capillary inner surface the microreactor that the oxide carried type noble metal catalyst of one deck is configured for the reaction of methyl alcohol anaerobic dehydrogenation;
Oxide carried type noble metal catalyst, oxide carrier is MgO, CeO
2, ZnO, La
2o
3, one or more in CuO; Described noble metal is one or more of metal in Au, Pd, Pt, Ru, Ag, and in catalyst, the load capacity of noble metal is 0.2-15wt%, preferred 0.5%-5.0wt%.
2., according to microreactor according to claim 1, it is characterized in that:
Described quartz capillary nozzle diameter is 0.5-5mm;
Described oxide carried type noble metal catalyst layer thickness is 0.02-0.2mm.
3. a preparation method for microreactor described in claim 1 or 2, is characterized in that:
Capillary microreactor preparation can be performed as follows:
(a) capillary tube inner wall amination process:
At 300-800 DEG C of temperature, ammonia is passed through quartz capillary with 5-50mL/min flow velocity, process 1-48h; Preferred 500-800 DEG C, ammonia flow velocity 10-30mL/min, process 6-12h;
(b) carrier metal ion and precious metal ion eutectoid content:
Flow through the quartz capillary after amination process in the carrier metal ion of required ratio and precious metal ion solution by constant-flux pump, carrier metal ion and precious metal ion are adsorbed on capillary tube inner wall by quartz capillary inwall amino; The load capacity of noble metal is regulated and controled by the ratio controlling carrier metal ion and precious metal ion;
(c) high-temperature process:
Under air, 200-600 DEG C processes 1-12h to quartz capillary after step (b) being processed; Preferred 300-500 DEG C of process 3-6h; The noble metal catalyst obtaining Metal Supported is deposited on capillary tube inner wall, obtains capillary microreactor.
4., according to the preparation method of microreactor described in claim 3, it is characterized in that:
Carrier metal ion and precious metal ion solution are one in the nitrate of metal, sulfate, chlorate, acetate or two or more; Concentration 0.1-5mol/L; Preferred 0.5-1mol/L;
The flow velocity flowing through quartz capillary is 0.1-5mL/min, and the time is 1-48h.
5. an application for microreactor described in claim 1 or 2, is characterized in that:
Described microreactor is applied in methyl alcohol anaerobic dehydrogenation, and under the condition of 100-400 DEG C, methyl alcohol anaerobic dehydrogenation obtains anhydrous formaldehyde.
6., according to the application of microreactor described in claim 5, it is characterized in that:
Adopt quartz capillary described in claim 1 or 2 to be microreactor, product adopts on-line measuring device analysis; First use argon gas purge, the air that removing inside retains and impurity, carry out being preheating to reaction temperature under argon shield; Take argon gas as carrier gas, wherein the volume content of methyl alcohol in methyl alcohol and argon gas gaseous mixture is 10%-60%; Reaction temperature is 100-400 DEG C; Flow rate of carrier gas is 5-100mLmin
-1.
7., according to the application of microreactor described in claim 6, it is characterized in that:
Particular methanol volume content is 35%-55%; Reaction temperature is 200-300 DEG C; The mass space velocity of bed is preferably 5-80mLg
-1 cats
-1, be preferably 20-55mLmin
-1.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112871103A (en) * | 2021-01-14 | 2021-06-01 | 浙江工业大学 | Preparation method of capillary microchannel reactor with internal coated hydrotalcite film |
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|---|---|---|---|---|
| WO2004103550A1 (en) * | 2003-05-16 | 2004-12-02 | Velocys Inc. | Microchannel with internal fin support for catalyst or support medium |
| CN102274722A (en) * | 2011-06-17 | 2011-12-14 | 中国科学院福建物质结构研究所 | V2O3 for preparing anhydrous formaldehyde by directly dehydrogenizing methanol as well as supported V2O3 catalyst and preparation method thereof |
| CN102941112A (en) * | 2012-11-21 | 2013-02-27 | 常州大学 | Novel catalyst for dehydrogenation preparation of formaldehyde by using methyl alcohol, preparation method and application of novel catalyst |
| CN103111238A (en) * | 2012-12-07 | 2013-05-22 | 北京航天试验技术研究所 | Novel method for applying methyl alcohol dehydrogenation reaction to endothermic fuel |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103550A1 (en) * | 2003-05-16 | 2004-12-02 | Velocys Inc. | Microchannel with internal fin support for catalyst or support medium |
| CN102274722A (en) * | 2011-06-17 | 2011-12-14 | 中国科学院福建物质结构研究所 | V2O3 for preparing anhydrous formaldehyde by directly dehydrogenizing methanol as well as supported V2O3 catalyst and preparation method thereof |
| CN102941112A (en) * | 2012-11-21 | 2013-02-27 | 常州大学 | Novel catalyst for dehydrogenation preparation of formaldehyde by using methyl alcohol, preparation method and application of novel catalyst |
| CN103111238A (en) * | 2012-12-07 | 2013-05-22 | 北京航天试验技术研究所 | Novel method for applying methyl alcohol dehydrogenation reaction to endothermic fuel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112871103A (en) * | 2021-01-14 | 2021-06-01 | 浙江工业大学 | Preparation method of capillary microchannel reactor with internal coated hydrotalcite film |
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