CN103043607A - Method and device for catalytic preparation of hydrogen from naphthenic hydrocarbon - Google Patents
Method and device for catalytic preparation of hydrogen from naphthenic hydrocarbon Download PDFInfo
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- CN103043607A CN103043607A CN2013100143551A CN201310014355A CN103043607A CN 103043607 A CN103043607 A CN 103043607A CN 2013100143551 A CN2013100143551 A CN 2013100143551A CN 201310014355 A CN201310014355 A CN 201310014355A CN 103043607 A CN103043607 A CN 103043607A
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Abstract
The invention provides a method and a device for catalytic preparation of hydrogen from naphthenic hydrocarbon. The method comprises the following steps of: fixing a catalyst at the bottom of a reactor after the catalyst is washed by absolute ethyl alcohol; vacuumizing the reactor and introducing nitrogen into the reactor; heating the bottom of the reactor under nitrogen protection to ensure that the temperature of the catalyst slowly rises; stopping introducing the nitrogen after the catalyst is dried to open an organic liquid condenser; setting a dehydrogenation reaction temperature; heating the bottom of the reactor to be the dehydrogenation reaction temperature; injecting and feeding the naphthenic hydrocarbon at a constant velocity; discharging the generated hydrogen from the system after condensation and separation; and condensing the other steam components in a condenser and gathering the components into a product storage tank. By the method and the device, a precious metal catalyst is replaced by cheap raney nickel, so that the reaction cost is reduced, and the catalytic effect of the catalyst is good; the feeding is carried out in a jetting mode under a wet-and-dry multi-phase reaction condition, so that the dehydrogenation reaction efficiency is improved; and the gas is not needed to be carried or blown, the prepared hydrogen is high in purity and not needed to be separated again.
Description
Technical field
The present invention relates to utilize the organic liquid hydrogen preparation field, relate in particular to a kind of " wet-do " thus utilize catalyzer to make the method and apparatus of naphthenic hydrocarbon continuous dehydrogenation hydrogen making under the multi phase state reaction conditions.
Background technology
Hydrogen Energy as a kind of green energy resource have cleaning, renewable, the source is abundant, the utilization ratio advantages of higher, Hydrogen Energy is also thought the tool potentiality new cleaning fuel of substitute fossil fuels widely simultaneously.The development and use of Hydrogen Energy also can well be alleviated because excessively discharging CO
-2And the Greenhouse effect that cause.But the volume energy density of Hydrogen Energy is very low, therefore, seek suitable storage hydrogen carrier and mention energy density to improve it, and resolve the storage hydrogen carrier storage, to put the hydrogen technology be the major issue that hydrogen energy source is moved towards practical engineering application.
Organic liquid storage hydrogen has obtained people's extensive concern as a kind of efficient storage hydrogen mode.Organic liquid storage hydrogen is by the storage that the reversible reaction of organic liquid shortening and dehydrogenation is realized hydrogen, puts, and has the hydrogen-storage amount height, and transportation safety is convenient, and reactant and product the advantage such as can reuse, and is a very promising hydrogen storage technology.In fact, the process of organic liquid hydride hydrogenation and dehydrogenation all is catalyzed reaction, and the condition of reaction and the performance of catalyzer are determining the efficient of reaction to a great extent.
Traditional organic liquid hydride dehydrogenation mainly contains liquid dehydrogenation reaction and gaseous state dehydrogenation reaction.From thermodynamics, the organic liquid catalytic dehydrogenation is thermo-negative reaction, and high temperature is conducive to dehydrogenation reaction and occurs, and can only reach boiling of reactant and the temperature of catalyzer is the highest in the liquid dehydrogenation reaction, to reacting unfavorable.Driven mechanics angle, organic liquid catalytic dehydrogenation are reversible reactions, are easy to occur reversed reaction under liquid dehydrogenation reaction conditions, cause the dehydrogenation effect to descend.Under traditional dehydrogenation reaction technical qualification, utilize P
-The precious metals such as t, Pd, the Rh mixed catalyst that extremely mixes is although can obtain preferably dehydrogenation effect, the easy coking of catalyzer, inactivation, the persistence of reaction is bad, and catalyzer is expensive, the reaction unit volume is comparatively huge, is not suitable for producing on a large scale the application of hydrogen.Therefore reaction conditions and the economic and practical catalyzer of seeking a kind of efficient stable are the main directions of organic liquid catalyzing manufacturing of hydrogen technical study.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, a kind of method and device of naphthenic hydrocarbon catalyzing manufacturing of hydrogen is provided.
The objective of the invention is to be achieved through the following technical solutions: a kind of method of naphthenic hydrocarbon catalyzing manufacturing of hydrogen, the method may further comprise the steps:
Step 1: get the catalyzer Raney's nickel of 3-7 g, to displace moisture wherein, then the catalyzer Raney's nickel is pressed into round sheet with absolute ethanol washing, be fixed in reactor bottom;
Step 2: reactor is vacuumized, then pass into nitrogen in reactor, reactor heating bottom under nitrogen protection makes catalyzer be warming up to 160 ℃ with the temperature rise rate of 10 ℃/min, remove in the Raney's nickel in conjunction with water and dehydrated alcohol, stop logical nitrogen;
Step 3: continue reactor bottom is heated to 315-346 ℃ of dehydrogenation reaction temperature, open syringe pump after catalyst temperature stabilization, naphthenic hydrocarbon is cooled to that the constant rate of speed with 1.75-1.81ml/min is injected into catalyst surface and dehydrogenation reaction occurs after 2-10 ℃; In the reaction process, the reactor bottom temperature-stable is at 315-346 ℃; Described naphthenic hydrocarbon can be selected hexanaphthene, methylcyclohexane or perhydronaphthalene;
Step 4: the gas that reaction produces is collected after condensation.
A kind of device of naphthenic hydrocarbon catalyzing manufacturing of hydrogen, it comprises: nitrogengas cylinder, organic liquid hold-up vessel, organic liquid condenser, syringe pump, vacuum pump, nitrogen stopping valve, nozzle, reactor, resistive heater, stopping valve, temperature controller, phlegma storage tanks, condenser and valve; Wherein, described nitrogengas cylinder links to each other with reactor by the nitrogen transfer lime, and the nitrogen stopping valve is installed on the nitrogen transfer lime; The inlet mouth of vacuum pump links to each other with reactor, mounted valve on the air outlet; Organic liquid hold-up vessel, organic liquid condenser link to each other successively with syringe pump, and syringe pump links to each other with the nozzle that is positioned at reactor inlet by the organic liquid transfer lime, and resistive heater is fixed on the bottom of reactor, and links to each other with temperature controller; Reactor links to each other with condenser by air shooter, and stopping valve is installed on the air shooter, and the bottom of condenser links to each other with the phlegma storage tanks by the condensed fluid transfer lime, and hydrogen delivery tube is installed at the top of condenser.
The invention has the beneficial effects as follows that the present invention replaces noble metal catalyst with comparatively cheap Raney's nickel, reduced reaction cost, and catalyst is effective; With the method charging of spraying, under " wet-as to do " multi phase state reaction conditions, carry out, improved dehydrogenation reaction efficient; Without carrier gas or sweep gas, the hydrogen purity of producing is high, need not to separate again.This method is by ingenious control and intervention to dynamic power balance in the reaction process, make organic liquid hydride after arriving catalyst surface, form liquid film, and occur " Gu liquid-" dehydrogenation reaction, the reactant that the product Buddhist monk that then will just generate by the catalyst surface heat does not have enough time to react evaporates away, make it break away from catalyzer, effectively stoped the generation of reversed reaction, the hydrogen of generation is then separated from reaction system by condensation.This method has been utilized replacing of catalyst surface " wet-as to do " multi phase state, both guaranteed carrying out smoothly of naphthenic hydrocarbon dehydrogenation reaction, can suppress contingent reversed reaction by the forced evaporation that generates product again, greatly improved the dehydrogenation reaction reaction efficiency, thereby obtain higher conversion rate of dehydrogenation, can avoid the generation of catalyst surface coking phenomenon simultaneously.
Description of drawings
Fig. 1 is apparatus structure synoptic diagram of the present invention.
Among the figure, nitrogengas cylinder 1, organic liquid hold-up vessel 2, organic liquid condenser 3, syringe pump 4, vacuum pump 5, nitrogen stopping valve 6, nozzle 7, reactor 8, resistive heater 9, stopping valve 10, catalyzer 11, temperature controller 12, phlegma storage tanks 13, condenser 14, nitrogen transfer lime 15, vacuum-pumping tube 16, organic liquid transfer lime 17, air shooter 18, condensed fluid transfer lime 19, hydrogen delivery tube 20, valve 21.
Embodiment
The method of naphthenic hydrocarbon catalyzing manufacturing of hydrogen of the present invention may further comprise the steps
Step 1: get the catalyzer Raney's nickel of 3-7 g, to displace moisture wherein, then the catalyzer Raney's nickel is pressed into round sheet with absolute ethanol washing, be fixed in reactor bottom.
Step 2: reactor is vacuumized, then pass into nitrogen in reactor, reactor heating bottom under nitrogen protection makes catalyzer be warming up to 160 ℃ with the temperature rise rate of 10 ℃/min, remove in the Raney's nickel in conjunction with water and dehydrated alcohol, stop logical nitrogen.
Step 3: continue reactor bottom is heated to 315-346 ℃ of dehydrogenation reaction temperature, open syringe pump after catalyst temperature stabilization, naphthenic hydrocarbon is cooled to that the constant rate of speed with 1.75-1.81ml/min is injected into catalyst surface and dehydrogenation reaction occurs after 2-10 ℃; In the reaction process, the reactor bottom temperature-stable is at 315-346 ℃.Described naphthenic hydrocarbon can be selected hexanaphthene, methylcyclohexane or perhydronaphthalene.
Step 4: the gas that reaction produces is collected after condensation.
As shown in Figure 1, the device of naphthenic hydrocarbon catalyzing manufacturing of hydrogen of the present invention comprises: nitrogengas cylinder 1, organic liquid hold-up vessel 2, organic liquid condenser 3, syringe pump 4, vacuum pump 5, nitrogen stopping valve 6, nozzle 7, reactor 8, resistive heater 9, stopping valve 10, temperature controller 12, phlegma storage tanks 13, condenser 14 and valve 21.
Nitrogengas cylinder 1 links to each other with reactor 8 by nitrogen transfer lime 15, and nitrogen stopping valve 6 is installed on the nitrogen transfer lime 15; The inlet mouth of vacuum pump 5 links to each other with reactor 8, and mounted valve 21 on the air outlet; Organic liquid hold-up vessel 2, organic liquid condenser 3 and syringe pump 4 link to each other successively, and syringe pump 4 links to each other with the nozzle 7 that is positioned at reactor 8 entrances by organic liquid transfer lime 17, and resistive heater 9 is fixed on the bottom of reactor 8, and links to each other with temperature controller 12; Reactor 8 links to each other with condenser 14 by air shooter 18, and stopping valve 10 is installed on the air shooter 18, and the bottom of condenser 14 links to each other with phlegma storage tanks 13 by condensed fluid transfer lime 19, and hydrogen delivery tube 20 is installed at the top of condenser 14.
Below by embodiment the present invention is carried out concrete description; only be used for the present invention is further specified; can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
Get the catalyzer Raney's nickel of 3 g, displacing moisture wherein, and catalyzer is pressed into round sheet with absolute ethanol washing 3 times, then add in the reactor of 50ml, and be fixed in reactor bottom; Opening vacuum pump vacuumizes reactor, close vacuum pump, open nitrogengas cylinder, in reactor, pass into nitrogen, reactor heating bottom under nitrogen protection, catalyzer is slowly heated up, temperature rise rate is 10 ℃/min, remove in the Raney's nickel in conjunction with water and dehydrated alcohol, catalyzer is dried when treating that temperature rises to 160 ℃, stop logical nitrogen this moment, open the organic liquid condenser hexanaphthene is cooled to 6 ℃; Set 326 ℃ of dehydrogenation reaction temperature, and reactor bottom is heated to the dehydrogenation reaction temperature, open syringe pump after catalyst temperature stabilization, hexanaphthene (analytical pure) is injected into catalyst surface and dehydrogenation reaction occurs with the constant rate of speed charging of 1.81ml/min.In the reaction process, be stabilized in the initial setting temperature by what the precise temperature control instrument made the reactor bottom temperature.The micro-molecular gas that reaction generates combines in the product storage tank after all the other steam group lease making condenser condenses by discharge system after the condensation separation.Measure to such an extent that the maximum hydrogen-producing speed of unit surface catalyzer is 0.36 mmol/min ﹒ cm
2, the product hydrogen purity is 96.31%.
Embodiment 2
Get the catalyzer Raney's nickel of 4.6g, displacing moisture wherein, and catalyzer is pressed into round sheet with absolute ethanol washing 3 times, then add in the reactor of 50ml, and be fixed in reactor bottom; Opening vacuum pump vacuumizes reactor, close vacuum pump, open nitrogengas cylinder, in reactor, pass into nitrogen, reactor heating bottom under nitrogen protection, catalyzer is slowly heated up, temperature rise rate is 10 ℃/min, remove in the Raney's nickel in conjunction with water and dehydrated alcohol, catalyzer is dried when treating that temperature rises to 160 ℃, stop logical nitrogen this moment, open the organic liquid condenser methylcyclohexane is cooled to 10 ℃; Set 315 ℃ of dehydrogenation reaction temperature, and reactor bottom is heated to the dehydrogenation reaction temperature, open syringe pump after catalyst temperature stabilization, methylcyclohexane (analytical pure) is injected into catalyst surface and dehydrogenation reaction occurs with the constant rate of speed charging of 1.75ml/min.In the reaction process, be stabilized in the initial setting temperature by what the precise temperature control instrument made the reactor bottom temperature.The micro-molecular gas that reaction generates combines in the product storage tank after all the other steam group lease making condenser condenses by discharge system after the condensation separation.Measure to such an extent that the maximum hydrogen-producing speed of unit surface catalyzer is 0.39mmol/min ﹒ cm
2, the product hydrogen purity is 96.27%.
Embodiment 3
(apparent density is about 3.0g ﹒ cm to get the catalyzer Raney's nickel of 7 g
-3, mean particle size 16.58 μ m), displacing moisture wherein, and catalyzer is suppressed circular thin layer with absolute ethanol washing 3 times, then add in the reactor of 50ml, and be fixed in reactor bottom; Opening vacuum pump vacuumizes reactor, close vacuum pump, open nitrogengas cylinder, in reactor, pass into nitrogen, reactor heating bottom under nitrogen protection, catalyzer is slowly heated up, temperature rise rate is 10 ℃/min, remove in the Raney's nickel in conjunction with water and dehydrated alcohol, catalyzer is dried when treating that temperature rises to 160 ℃, stop logical nitrogen this moment, open the organic liquid condenser perhydronaphthalene is cooled to 2 ℃; Set 346 ℃ of dehydrogenation reaction temperature, and reactor bottom is heated to the dehydrogenation reaction temperature, open syringe pump after catalyst temperature stabilization, perhydronaphthalene (analytical pure) is injected into catalyst surface and dehydrogenation reaction occurs with the constant rate of speed charging of 1.78ml/min.In the reaction process, be stabilized in the initial setting temperature by what the precise temperature control instrument made the reactor bottom temperature.The micro-molecular gas that reaction generates combines in the product storage tank after all the other steam group lease making condenser condenses by discharge system after the condensation separation.Measure to such an extent that the maximum hydrogen-producing speed of unit surface catalyzer is 0.37mmol/min ﹒ cm
2, the product hydrogen purity is 97.61%.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (2)
1. the method for a naphthenic hydrocarbon catalyzing manufacturing of hydrogen is characterized in that, the method may further comprise the steps
Step 1: get the catalyzer Raney's nickel of about 3-7 g, to displace moisture wherein, then the catalyzer Raney's nickel is pressed into round sheet with absolute ethanol washing, be fixed in reactor bottom;
Step 2: reactor is vacuumized, then pass into nitrogen in reactor, reactor heating bottom under nitrogen protection makes catalyzer be warming up to 160 ℃ with the temperature rise rate of 10 ℃/min, remove in the Raney's nickel in conjunction with water and dehydrated alcohol, stop logical nitrogen;
Step 3: continue reactor bottom is heated to 315-346 ℃ of dehydrogenation reaction temperature, open syringe pump after catalyst temperature stabilization, naphthenic hydrocarbon is cooled to that the constant rate of speed with 1.75-1.81ml/min is injected into catalyst surface and dehydrogenation reaction occurs after 2-10 ℃; In the reaction process, the reactor bottom temperature-stable is at 315-346 ℃; Described naphthenic hydrocarbon can be selected hexanaphthene, methylcyclohexane or perhydronaphthalene;
Step 4: the gas that reaction produces is collected after condensation.
2. the device of a naphthenic hydrocarbon catalyzing manufacturing of hydrogen, it is characterized in that it comprises: nitrogengas cylinder (1), organic liquid hold-up vessel (2), organic liquid condenser (3), syringe pump (4), vacuum pump (5), nitrogen stopping valve (6), nozzle (7), reactor (8), resistive heater (9), stopping valve (10), temperature controller (12), phlegma storage tanks (13), condenser (14) and valve (21) etc.; Wherein, described nitrogengas cylinder (1) links to each other with reactor (8) by nitrogen transfer lime (15), the upper nitrogen stopping valve (6) of installing of nitrogen transfer lime (15); The inlet mouth of vacuum pump (5) links to each other with reactor (8), mounted valve on the air outlet (21); Organic liquid hold-up vessel (2), organic liquid condenser (3) and syringe pump (4) link to each other successively, syringe pump (4) links to each other with the nozzle (7) that is positioned at reactor (8) entrance by organic liquid transfer lime (17), resistive heater (9) is fixed on the bottom of reactor (8), and links to each other with temperature controller (12); Reactor (8) links to each other with condenser (14) by air shooter (18), the upper stopping valve (10) of installing of air shooter (18), the bottom of condenser (14) links to each other with phlegma storage tanks (13) by condensed fluid transfer lime (19), and hydrogen delivery tube (20) is installed at the top of condenser (14).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104310309A (en) * | 2014-10-20 | 2015-01-28 | 浙江大学 | Catalytic hydrogen production method and device suitable for hydrogen energy automobile |
| CN106050480A (en) * | 2016-07-06 | 2016-10-26 | 浙江大学 | Liquid organic hydride based onboard hydrogen supply system applicable to hydrogen energy automobile |
| CN112999992A (en) * | 2019-12-20 | 2021-06-22 | 中国科学院理化技术研究所 | Dehydrogenation reaction system of thermocatalytic organic liquid hydrogen storage material and preparation method and application thereof |
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| CN203095609U (en) * | 2013-01-16 | 2013-07-31 | 浙江大学 | Cycloalkane-catalyzed hydrogen production device |
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| NOBUKO KARIYA ET AL.: "Efficient hydrogen production using cyclohexane and decalin by pulse-spray mode reactor with Pt catalysts", 《APPLIED CATALYSIS》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310309A (en) * | 2014-10-20 | 2015-01-28 | 浙江大学 | Catalytic hydrogen production method and device suitable for hydrogen energy automobile |
| CN104310309B (en) * | 2014-10-20 | 2016-08-24 | 浙江大学 | A kind of method and device of the catalyzing manufacturing of hydrogen being applicable to hydrogen energy automobile |
| CN106050480A (en) * | 2016-07-06 | 2016-10-26 | 浙江大学 | Liquid organic hydride based onboard hydrogen supply system applicable to hydrogen energy automobile |
| CN106050480B (en) * | 2016-07-06 | 2018-09-14 | 浙江大学 | The vehicle-mounted hydrogen-feeding system of liquid organic hydride suitable for hydrogen energy automobile |
| CN112999992A (en) * | 2019-12-20 | 2021-06-22 | 中国科学院理化技术研究所 | Dehydrogenation reaction system of thermocatalytic organic liquid hydrogen storage material and preparation method and application thereof |
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Application publication date: 20130417 |