CN110013839A - It is a kind of to carry out the integrated method and its application of catalyst in micro passage reaction - Google Patents
It is a kind of to carry out the integrated method and its application of catalyst in micro passage reaction Download PDFInfo
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- CN110013839A CN110013839A CN201910381932.8A CN201910381932A CN110013839A CN 110013839 A CN110013839 A CN 110013839A CN 201910381932 A CN201910381932 A CN 201910381932A CN 110013839 A CN110013839 A CN 110013839A
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- catalyst
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of to carry out the integrated method of catalyst in micro passage reaction, comprising: catalyst is put into micro passage reaction bottom-heated to fusing and obtains liquid catalyst；Then the inner wall that the liquid catalyst of acquisition is blown to micro passage reaction is formed liquid catalyst liquid film by way of bottom inflow by using gas can be completed the integrated of micro passage reaction and catalyst.Micro passage reaction catalyst integrated approach provided by the present invention is applied to the reaction of boron oxide catalysis preparing propene by oxidative dehydrogenation of propane, olefine selective may be up to 95%.Micro passage reaction catalyst integrated approach provided by the present invention is simple and easy to operate, integrates high-efficient, solves the problems, such as the integrated difficulty of existing micro passage reaction catalyst.Micro passage reaction used in the present invention can react the heat of reaction generated with fast transfer, guarantee that reaction is completed under constant temperature conditions, to improve the selectivity of alkanes oxidative dehydrogenation reaction, application prospect is very wide.
Description
Technical field
The invention belongs to the applied technical fields of micro passage reaction, and in particular to one kind carries out in micro passage reaction
The integrated method and its application of catalyst.
Background technique
Micro passage reaction originates from microelectronic industry, is in the research side that the nineties in last century starts to rapidly develop
To (Zheng Yafeng, Zhaoyang, the research of Xin Feng microreactor and prospect [J] chemical industry progress, 2004 (05): 461-467).Microchannel plate
It answers device most important and is most intuitively characterized in that its inner passage size is other in the micron-scale, it is generally recognized that the feature of micro passage reaction
Size is between 10~1000 μm (on developmental research progress [J] of Ling Fang, Gu little Yan, Ke Dehong, Wang Tao micro passage reaction
Extra large chemical industry, 2017,42 (04): 35-38).Micro passage reaction has many advantages: for example, heat and mass is fast, highly-safe and can
Number increases amplification etc.；But due to being limited by its size, micro passage reaction catalyst filling is usually relatively difficult.Common catalyst
Filling technique has packed bed reactor technology and coating technology, further, it is also possible to which reactor is made of active material or by living
The modes such as microchannel are made to improve micro passage reaction (Chen G, Li S, Yuan Q.Pd-Zn/Cu-Zn-Al in property material
catalysts prepared for methanol oxidation reforming in microchannel reactors
[J] .Catalysis Today, 2007,120 (1): 63-70).
Packed bed reactor is by catalyst tabletting and to be sized to certain mesh number, by selecting spherical and suitable catalyst
Catalyst is directly filled in micro passage reaction after particle, the contacting efficiency of this filling mode reaction gas and catalyst
Height, but generally large (Yube K, Furuta M, the Mae K.Selective oxidation of phenol of bed pressure drop
with hydrogen peroxide using two types of catalytic microreactor[J].Catalysis
Today, 2007,125 (1-2): 56-63).Catalyst is integrated to be referred to and fixes catalyst and ensemble, common method have object
It manages directly painting method, chemical etching method or reactor or microchannel is manufactured by active material.It is by catalyst that physics, which directly coats,
The direct physics of solution is made with binder and is coated to micro passage reaction inner wall (Chu B, An H, Chen X, et
Al.Phase-pure M1 MoVNbTeOx, catalysts with tunable particle size for oxidative
Dehydrogenation of ethane [J] .Applied Catalysis A General, 2016,524:56-65), physics
The catalyst coat bed pressure drop of direct coating method preparation is small, but the uniformity of coating is not easy to control and is easy to peel off；Change
Etching method, which refers to, is integrated into microchannel for active component by the methods of wet etching for reactor wall surface or reaction channel
Reactor wall surface (Chen G, Li S, Yuan Q.Pd-Zn/Cu-Zn-Al catalysts prepared for methanol
Oxidation reforming in microchannel reactors [J] .Catalysis Today, 2007,120 (1):
63-70), than stronger, the coating for solving the problems, such as that physics coats is easy to fall off this method coating, but is operated more multiple
Miscellaneous and cost is also relatively high；It is reactivity by the reactor or microchannel, microchannel wall surface material of active material manufacture
Position (Kestenbaum H, Oliveira ALD, Schmidt W, et al.Silver-Catalyzed Oxidation of
Ethylene to Ethylene Oxide in a Microreaction System[J].Industrial&
Engineering Chemistry Research, 2005,41 (4): 710-719), although this mode operation is relatively simple,
But the selection of material but has significant limitation.
Summary of the invention
Place in view of the deficiency of the prior art, it is an object of that present invention to provide one kind in micro passage reaction
Carry out the integrated method and its application of catalyst.
In order to achieve the above objectives, solution of the invention is:
A method of catalyst is carried out in micro passage reaction and is integrated, and is specifically comprised the following steps:
(1) catalyst is put into micro passage reaction and is heated to fusing acquisition liquid catalyst；
(2) liquid catalyst obtained in step (1) is blown to microchannel plate by way of bottom inflow by using gas
Answering the inner wall of device to form liquid catalyst liquid film can be integrated to catalyst on the inner wall of micro passage reaction.
A kind of application carrying out the integrated method of catalyst in micro passage reaction in preparing propene by oxidative dehydrogenation of propane,
Specifically comprise the following steps:
(1) boron oxide is put into heating fusing in micro passage reaction and obtains liquid oxidatively B catalyst；
(2) the liquid oxidatively boron obtained in step (1) is blown to microchannel plate by way of bottom inflow by using gas
The inner wall of device is answered to form liquid oxidatively boron liquid film；
(3) reactor feed gas being made of propane and oxidant is passed into micro passage reaction and shape in step (2)
At liquid oxidatively boron liquid film contact and carry out preparing propene by oxidative dehydrogenation of propane, wherein reaction temperature is 550 DEG C, reaction pressure
For 1atm, reaction raw materials gas velocity is 30ml/min.
Preferably, the oxidant is selected from one of oxygen or air or two kinds mix.
Preferably, the volume ratio of the oxidant and alkane is 1: 1.
Preferably, gas described in step (2) is reaction gas or diluent gas.
The principle of the present invention is as follows:
Some researches show that non-metallic catalyst h-BN is used to oxidative dehydrogenation of propane reaction to obtain higher alkene choosing
Selecting property (Grant J T, Carrero C A, Goeltl F, et al.Selective oxidative dehydrogenation
Of propane to propene using boron nitride catalysts [J] .Science, 2016,354
(6319): 108043444 A of 1570-1573, CN), viewpoint points out that h-BN is catalyzed oxidative dehydrogenation of propane alkene recently
Active site be BOx (Grant J T, Mcdermott W P, Venegas J M, et al.Boron and Boron-
containing Catalysts for the Oxidative Dehydrogenation of Propane[J]
.ChemCatChem, 2017)；We consult B2O3Physical data discovery, the fusing point of the substance is about 450 DEG C, and existing special
Benefit report liquid oxidatively boron can directly be catalyzed low-carbon alkanes selective oxidation alkene (108484349 A of CN).There are also document reports
Falling liquid film micro passage reaction is used for if liquid is to CO by road2Gas absorbs, and has the advantages of high mass transfer ability and low pressure drop
(Zhang H, Chen G, Yue J, et al.Hydrodynamics and Mass Transfer of Gas-Liquid
Flow in a Failing Film Microreactor [J] .Aiche Journal, 2009,55 (5): 1110-1120；Yue
J, Chen G, Yuan Q, et al.Hydrodynamics and mass transfer characteristics in gas-
liquid flow through a rectangular microchannel[J].Chemical Engineering
Science, 2007,62 (7): 2096-2108)；In addition, there are also document reports recently carries out gas-liquid two-phase using liquid catalyst
Chemical reaction, play the role of good heat transfer medium (Ab á nades, Alberto, Mehravaran K, Rathnam R
K, et al.Hydrogen production via methane pyrolysis in a liquid metal bubble
Column reactor with a packed bed [J] .Chemical Engineering Journal, 2016,299:
192-200；D.Chester Upham, Vishal Agarwal, Alexander Khechfe, Zachary R.Snodgrass,
Michael J.Gordon, HoriaMetiu, Eric W.McFarland.Catalytic molten metals for the
Direct conversion of methane to hydrogen and separable carbon.Science, 2017,
358 (6365): 917-921).
Therefore, difficult problem is integrated for catalyst filling in micro passage reaction, it is proposed that a kind of catalyst collection
At scheme, selective oxidation boron forms catalyst liquid film as catalyst, in micro passage reaction wall surface, can be applied to low-carbon
In the oxidative dehydrogenation of alkane, have the advantages that heat and mass ability is strong, pressure drop is small and catalyst filling integrate it is convenient.It will urge
Agent is put into micro passage reaction, sees Fig. 1 (a)；Heating response device to catalyst becomes liquid, sees Fig. 1 (b)；Then it uses
Gas will be formed by liquid catalyst in such a way that bottom is fed and be blown to reactor wall face and drawout, see Fig. 1 (c)；
It is finally passed through the reactor feed gas containing propane and contacts progress oxidative dehydrogenation with the liquid oxidatively B catalyst on wall surface, see
Fig. 1 (d).Since catalysis oxidative dehydrogenation of propane reaction is that strong exothermal reaction can maintain oxidation B catalyst to be constantly in liquid,
And boron oxide is the activated centre of oxidative dehydrogenation of propane reaction, can greatly increase catalyst and reactor feed gas in this way
Contact area, to obtain raising catalytic reaction activity.
Advantages of the present invention:
1) catalyst can be integrated on micro passage reaction by the present invention by simply heating and ventilating, and integrate efficiency
Height, solving existing micro passage reaction because channel size limits, difficult and bed pressure drop is big to ask so that catalyst is filled
Topic.
2) micro passage reaction used in the present invention can react the heat of reaction generated with fast transfer, guarantee that reaction exists
It is completed under constant temperature, thus when micro passage reaction catalyst integrated approach provided by the present invention is applied to catalysis propane
When oxidative dehydrogenation, the selectivity of alkanes oxidative dehydrogenation reaction can be improved, olefine selective may be up to 95%, application prospect
It is very wide.
Detailed description of the invention
Fig. 1 is the signal provided by the present invention that the integrated method and its application of catalyst are carried out in micro passage reaction
Figure.
Specific embodiment
Further below in conjunction with the embodiments with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, specific quality, reaction time in example
With the example that temperature, technological parameter etc. are also only in OK range, those skilled in the art is according to the present invention above-mentioned
Some nonessential modifications and adaptations that content is made all belong to the scope of protection of the present invention.Particular technique is not specified in embodiment
Or condition person, it is described technology or conditions or to be carried out according to the literature in the art according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be bought by market.
In all of the embodiments illustrated, the calculation method of conversion of propane and selectivity of product is such as on unit area boron oxide
Under: unit area boron oxide alkane conversion (%)=100 × (alkane molal quantity after alkane molal quantity-reaction before reacting)/(anti-
Alkane molal quantity × boron oxide gross area before answering)
Propylene Selectivity (%)=100 × generation supplied propylene/(alkane rubs after alkane molal quantity-reaction before reacting
That number)
CO selectivity (%)=100 × generation CO molal quantity/(alkane molal quantity after alkane molal quantity-reaction before reacting)
CO2Selectivity (%)=100 × generation CO2Molal quantity/(react alkane mole after preceding alkane molal quantity-reaction
Number)
Unit area boron oxide olefin yields (%)=alkane conversion (%) × olefine selective (the %)/total face of boron oxide
Product
Embodiment 1
Catalyst preparation: by 0.5g solid B2O3It is added in micro passage reaction；It is heated to temperature and reaches 550 DEG C of solids
Boron oxide has turned to liquid oxidatively boron；It is passed through reaction gas or carrier gas from reactor bottom, by liquid oxidatively B catalyst
It is blown to and sweeps micro passage reaction inner wall；Liquid oxidatively B catalyst will be attached to formation boron oxide on reactor wall face and urge
Agent liquid film (as shown in Figure 1)
Oxidative dehydrogenation active testing condition: the volume ratio of propane and oxygen is 1: 1 in material mixed gas, and nitrogen is carrier gas
Body；Reaction mixture gas volume ratio is propane: oxygen: nitrogen=1: 1: 8；The flow velocity of material mixed gas is 30ml/min, reaction temperature
Degree is 550 DEG C, pressure 1atm, uses gas chromatographic detection instrument reaction product after reaction, the results are shown in Table 1.
Test result: the conversion ratio of unit area boron oxide propane is 0.4%cm-2, Propylene Selectivity 95.3% do not have
Detect COx, unit area boron oxide propene yield is 0.4%cm-2。
Catalyst is carried out in 1. micro passage reaction of table integrates the catalytic activity for preparing propene by oxidative dehydrogenation of propane
Claims (5)
1. a kind of carry out the integrated method of catalyst in micro passage reaction, which comprises the following steps:
(1) catalyst is put into micro passage reaction and is heated to fusing acquisition liquid catalyst；
(2) liquid catalyst obtained in step (1) is blown to micro passage reaction by way of bottom inflow by using gas
Inner wall formed liquid catalyst liquid film catalyst can be integrated on the inner wall of micro passage reaction.
2. a kind of catalyst integrated method according to claim 1 that carries out in micro passage reaction takes off in oxidation of propane
Application in hydrogen propylene, which comprises the following steps:
(1) boron oxide is put into heating fusing in micro passage reaction and obtains liquid oxidatively B catalyst；
(2) the liquid oxidatively boron obtained in step (1) is blown to micro passage reaction by way of bottom inflow by using gas
Inner wall formed liquid oxidatively boron liquid film；
(3) reactor feed gas being made of propane and oxidant is passed into micro passage reaction and is formed in step (2)
Liquid oxidatively boron liquid film contacts and carries out preparing propene by oxidative dehydrogenation of propane, wherein reaction temperature is 550 DEG C, and reaction pressure is
1atm, reaction raw materials gas velocity are 30ml/min.
3. the catalyst integrated method according to claim 2 that carries out in micro passage reaction is in oxidative dehydrogenation of propane system
Application in propylene, it is characterised in that: the oxidant is selected from one of oxygen or air or two kinds mix.
4. the catalyst integrated method according to claim 2 that carries out in micro passage reaction is in oxidative dehydrogenation of propane system
Application in propylene, it is characterised in that: the volume ratio of the oxidant and propane is 1: 1.
5. the catalyst integrated method according to claim 2 that carries out in micro passage reaction is in oxidative dehydrogenation of propane system
Application in propylene, it is characterised in that: gas described in step (2) is reaction gas or diluent gas.
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| CN201910381932.8A CN110013839A (en) | 2019-05-08 | 2019-05-08 | It is a kind of to carry out the integrated method and its application of catalyst in micro passage reaction |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1589174A (en) * | 2001-12-05 | 2005-03-02 | 加利福尼亚大学董事会 | Chemical microreactor and method thereof |
| CN101060176A (en) * | 2006-04-19 | 2007-10-24 | 三星电机株式会社 | Catalyst filling method in micro-channels |
| CN101367695A (en) * | 2002-06-13 | 2009-02-18 | 维罗西股份有限公司 | Catalytic oxidative dehydrogenation and microchannel reactors for catalytic oxidative dehydrogenation |
| CN101579632A (en) * | 2009-03-24 | 2009-11-18 | 华东师范大学 | Nickel palladium/ silicon microchannel catalyst and application thereof on preparing electrode of integratable direct methanol fuel cell |
| CN106622057A (en) * | 2015-10-30 | 2017-05-10 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis microreactor and Fischer-Tropsch synthesis method |
| CN108484349A (en) * | 2018-02-28 | 2018-09-04 | 厦门大学 | A method of carrying out alkanes oxidative dehydrogenation alkene using liquid oxidatively B catalyst |
-
2019
- 2019-05-08 CN CN201910381932.8A patent/CN110013839A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1589174A (en) * | 2001-12-05 | 2005-03-02 | 加利福尼亚大学董事会 | Chemical microreactor and method thereof |
| CN101367695A (en) * | 2002-06-13 | 2009-02-18 | 维罗西股份有限公司 | Catalytic oxidative dehydrogenation and microchannel reactors for catalytic oxidative dehydrogenation |
| CN101060176A (en) * | 2006-04-19 | 2007-10-24 | 三星电机株式会社 | Catalyst filling method in micro-channels |
| CN101579632A (en) * | 2009-03-24 | 2009-11-18 | 华东师范大学 | Nickel palladium/ silicon microchannel catalyst and application thereof on preparing electrode of integratable direct methanol fuel cell |
| CN106622057A (en) * | 2015-10-30 | 2017-05-10 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis microreactor and Fischer-Tropsch synthesis method |
| CN108484349A (en) * | 2018-02-28 | 2018-09-04 | 厦门大学 | A method of carrying out alkanes oxidative dehydrogenation alkene using liquid oxidatively B catalyst |
Non-Patent Citations (2)
| Title |
|---|
| HARRY KESTENBAUM ET AL.: "Silver-Catalyzed Oxidation of Ethylene to Ethylene Oxide in a Microreaction System", 《IND. ENG. CHEM. RES.》 * |
| 贾启云等: "微通道内催化剂的制备", 《化工时刊》 * |
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Application publication date: 20190716 |