CN109589890A - A kind of hydrogen peroxide synthesizer and method - Google Patents
A kind of hydrogen peroxide synthesizer and method Download PDFInfo
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- CN109589890A CN109589890A CN201910027525.7A CN201910027525A CN109589890A CN 109589890 A CN109589890 A CN 109589890A CN 201910027525 A CN201910027525 A CN 201910027525A CN 109589890 A CN109589890 A CN 109589890A
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 127
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000010189 synthetic method Methods 0.000 claims abstract description 8
- 239000002082 metal nanoparticle Substances 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000013384 organic framework Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 239000001301 oxygen Substances 0.000 abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 abstract description 49
- 239000001257 hydrogen Substances 0.000 abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 33
- 238000004880 explosion Methods 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000012429 reaction media Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 11
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910002845 Pt–Ni Inorganic materials 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 210000003850 cellular structure Anatomy 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- -1 oxygen free radical Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 206010024769 Local reaction Diseases 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00835—Comprising catalytically active material
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00858—Aspects relating to the size of the reactor
- B01J2219/0086—Dimensions of the flow channels
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of hydrogen peroxide synthesizer and methods, belong to hydrogen peroxide technical field, solve the problems, such as following in the prior art: (1) hydrogen and oxygen feed mixed explosion range are wider, and danger coefficient is high；(2) hydrogen and oxygen solubility in reaction medium are smaller, and reaction efficiency is caused to be difficult to meet demand of industrial production；(3) hydrogen-oxygen directly generates water and hydrogen peroxide and the side reactions such as decomposes and causes selectivity of product low in reaction process.Micro passage reaction includes the substrate and cover plate mutually fastened, and substrate and cover plate form microchannel structure after fastening；The micro passage reaction includes feed zone, mixed zone and reaction zone, and reaction zone is coated with metal nanoparticle-metal organic framework hybridized film of sandwich structure.Hydrogen peroxide synthetic method includes the following steps: to be passed through H2、O2With reaction dissolvent → H2、O2With reaction dissolvent mix → produce H2O2.The present invention realizes the safety, high-quality, high efficiency production of hydrogen peroxide.
Description
Technical field
The present invention relates to hydrogen peroxide technical field more particularly to a kind of hydrogen peroxide synthesizer and methods.
Background technique
Hydrogen peroxide only generates oxygen and water in use, is a kind of environmentally friendly chemical products, can answer extensively
For industries such as chemical industry, weaving, papermaking, food, environmental protections.
The large-scale industrial production of hydrogen peroxide mostly uses anthraquinone at present, this method technology maturation, safety coefficient compared with
Height, but there are process flows it is complicated, plant investment is higher and environmental pollution is serious the problems such as.In recent years, novel peroxidating
Hydrogen synthetic method mainly includes hydrogen-oxygen direct synthesis technique, fuel cell method, plasma method and supercritical carbon dioxide process etc..By
The method of hydrogen and oxygen producing hydrogen peroxide by direct synthesis is based on ideal atom economic reaction, does not generate noxious material, have
Economical and efficient, environmentally protective advantage, were put forward for the first time from 1914 and are just concerned.Hydrogen-oxygen direct synthesis technique is commonly used to urge
Agent is load type metal catalyst, and common metal active component is Pd, Pt, Au etc..But since load type metal catalyst is living
Property component surface hydrogen-oxygen concentration limited by gas solubility, cause reaction rate compared with slow, hydrogen peroxide selectivity is lower.
In addition, the active component of load type metal catalyst is easy to happen reunion during the reaction, lead to effective active number of loci
Decline.
Hydrogen-oxygen producing hydrogen peroxide by direct synthesis faces following challenge in industrial applications at present: (1) hydrogen and oxygen feed
Mixed explosion range is wider, and danger coefficient is high；(2) hydrogen and oxygen solubility in reaction medium are smaller, lead to reaction efficiency
It is difficult to meet demand of industrial production；(3) hydrogen-oxygen directly generates water and hydrogen peroxide and the side reactions such as decomposes and causes to produce in reaction process
Object is selectively low.
Summary of the invention
In view of above-mentioned analysis, the present invention is intended to provide a kind of hydrogen peroxide synthesizer and method, are at least able to solve
One of following technical problem: (1) hydrogen and oxygen feed mixed explosion range are wider, and danger coefficient is high；(2) hydrogen and oxygen exist
Solubility is smaller in reaction medium, and reaction efficiency is caused to be difficult to meet demand of industrial production；(3) hydrogen-oxygen is directly raw in reaction process
The side reactions such as Cheng Shui and hydrogen peroxide decomposition cause selectivity of product low.
The purpose of the present invention is mainly achieved through the following technical solutions:
On the one hand, the present invention provides a kind of hydrogen peroxide synthesizer, the synthesizer includes micro passage reaction,
Including the substrate and cover plate mutually fastened, microchannel structure is formed after the substrate and cover plate fastening；
The micro passage reaction includes feed zone, mixed zone and reaction zone, and the feed zone includes gas feed and liquid
Body import, the reaction zone are coated with metal nanoparticle-metal organic framework hybridized film of sandwich structure；The sandwich
Structure are as follows: bottom and top layer are metal organic framework film, and intermediate sandwich of layers is metal nanoparticle.
The present invention has also done following improvement on the basis of above scheme:
Further, the channel width of the reaction zone is 0.1~1.0mm, 0.1~1.0mm of channel depth, and passage length is
20~60mm.
Further, the feed zone and/or the channel width of the mixed zone are 0.01~0.50mm, and channel depth is
0.01~0.50mm, passage length are 50~100mm.
Further, the metal center of the metal organic framework is one of Al, Zr, Cr, Fe, Zn or a variety of.
Further, the cellular structure of the metal organic framework is one of MIL, UIO, ZIF.
Further, the metal nanoparticle is one of Pt, Pd, Rh, Ru, Au, Ni, Co, Cu and Fe or a variety of；Institute
The load capacity for stating metal nanoparticle is metal nanoparticle-metal organic framework hybridized film gross mass 0.5%~10.0%.
Further, the quantity of the gas feed is two.
On the other hand, the present invention also provides a kind of metal nanoparticle of sandwich structure-metal organic framework hydridization
The preparation method of film: include the following steps:
Step 1: being formulated for preparing the precursor solution of metal organic framework and metal salt solution, by the two mixed in equal amounts
Obtain mixed solution；
Step 2: being passed through and be used to prepare into the microchannel of the described in any item hydrogen peroxide synthesizers of claim 1-7
The mixed solution of metal organic framework, it is dry, obtain underlying metal organic framework film；
Step 3: being formulated for preparing the metal salt solution of metal nanoparticle；
Step 4: preparing metal nanoparticle with liquid phase reduction and be coated on the underlying metal organic framework film of reaction zone
On；
Step 5: continue to be passed through the mixed solution for preparing metal organic framework into microchannel, coated metal nanoparticles,
It is dry, top-level metallic organic framework film is formed, the metal nanoparticle with sandwich structure-metal organic framework hydridization is obtained
Film.
In addition, including the following steps: the invention also discloses a kind of hydrogen peroxide synthetic method
(1) H is passed through into micro passage reaction by two gas feeds and liquid-inlet respectively2、O2And reaction dissolvent；
(2)H2、O2It is mixed in mixed zone with reaction dissolvent；
(3)H2And O2H is synthesized in reaction zone2O2；
(4)H2O2It is exported from product exit.
Further, O2And H2Velocity ratio be 1:1~4:1, reaction temperature be 40~120 DEG C, reaction pressure be 0.1~
2.5MPa。
The present invention has the beneficial effect that:
(1) present invention is by selecting metal nanoparticle-metal organic framework (NMPs-MOFs) hybridized film as catalysis
Agent, and NMPs-MOFs hybridized film is designed as sandwich structure, i.e. bottom is metal organic framework (MOFs) film, intermediate
Sandwich is metal nanoparticle (NMPs), the i.e. active site of catalyst, and top layer is MOFs film, 1. can effectively improve NMPs gold
Belong to active sites scattering of points, increases the catalytic activity of single locus；2. MOFs film can be by a certain percentage to reaction gas, that is, hydrogen
Gas and oxygen are adsorbed and are enriched with, to improve the local concentration of NMPs metal active site surface reactant, improve reaction
Efficiency；3. MOFs film has cell breath or unsatuated metal site, pass through the choosing of device to hole cage reaction gases concentration ratio
The control of selecting property is conducive to improve the selectivity of hydrogen peroxide.
(2) each interlayer structure unit can be regarded as a minisize reaction as catalyst by NMPs-MOFs hybridized film
Device realizes quasi- homogeneousization of heterogeneous catalysis, greatly improves catalytic reaction efficiency.
(3) present invention uses micro passage reaction and dynamics and heating power based on the reaction of hydrogen-oxygen producing hydrogen peroxide by direct synthesis
Characteristic is learned, on the basis for fully considering the key factors such as reaction system gas-phase feed, solvent environment, fluid rate and reaction efficiency
On, structure design has been carried out to micro passage reaction, by selecting suitable channel width, depth and length, has improved reaction
Efficiency.
(4) by being coated on micro passage reaction inner wall for NMPs-MOFs hybridized film as catalyst, it is straight to reduce gas-liquid-solid
A series of problems, such as connecing entrainment loss, the part channel, short circuit, dead angle of mixed system, takes full advantage of micro passage reaction
The growth mechanism of design feature and NMPs-MOFs hybridized film, the two is organically combined, improve entire reaction system stability and
Life cycle is conducive to industrialization promotion.
(5) width of microchannel and depth are far below the quenching distance of hydrogen and oxygen free radical in reactor, therefore can be with
Break hydrogen/oxygen molar ratio to be limited by traditional explosion limit, helps to improve the selectivity and reinforcement process of hydrogen peroxide
The safety of operation significantly improves the safety coefficient of synthesis technology.
(6) micro passage reaction it is light it is portable, can operation repetitive, it can be installed to online client needs place, keep away
Exempt from the danger in hydrogen peroxide transportational process, reduces cost.
(7) synthetic method of the invention has high Atom economy, operating safety factor height, reaction efficiency height, peroxidating
The advantages such as hydrogen quality height and product yield height.
It in the present invention, can also be combined with each other between above-mentioned each technical solution, to realize more preferred assembled schemes.This
Other feature and advantage of invention will illustrate in the following description, also, certain advantages can become from specification it is aobvious and
It is clear to, or understand through the implementation of the invention.The objectives and other advantages of the invention can be by specification, claims
Specifically noted content is achieved and obtained.
Detailed description of the invention
Attached drawing is only used for showing the purpose of specific embodiment, and is not to be construed as limiting the invention, in entire attached drawing
In, identical reference symbol indicates identical component.
Fig. 1 is the structural schematic diagram of micro passage reaction used in the embodiment of the present invention.
Specific embodiment
Specifically describing the preferred embodiment of the present invention with reference to the accompanying drawing, wherein attached drawing constitutes the application a part, and
Together with embodiments of the present invention for illustrating the principle of the present invention, it is not intended to limit the scope of the present invention.
A specific embodiment of the invention discloses a kind of micro passage reaction, including the substrate and lid mutually fastened
Piece, substrate and cover plate form microchannel structure after fastening.
Micro passage reaction includes feed zone, mixed zone and reaction zone, and feed zone includes 2 gas feeds and 1 liquid
Import, reaction zone are coated with the NMPs-MOFs hybridized film of sandwich structure；Sandwich structure are as follows: bottom and top layer are MOFs film,
Intermediate sandwich of layers is NMPs.
Compared with prior art, the micro passage reaction of this implementation significantly improves reaction efficiency and product yield, and
The safety coefficient of synthesis technology, is conducive to industrialization promotion
Specifically, the present embodiment, which passes through, selects NMPs-MOFs hybridized film as catalyst, and NMPs-MOFs is miscellaneous
Change film and be designed as sandwich structure, is i.e. bottom is MOFs film, and intermediate is sandwich for NMPs, the i.e. active site of catalyst, top layer
For MOFs film, the dispersion degree of NMPs metal active site 1. can effectively improve, increase the catalytic activity of single locus；②MOFs
Film can be adsorbed and be enriched with to reaction gas, that is, hydrogen and oxygen by a certain percentage, to improve NMPs metal active site table
The local concentration of face reactant improves reaction efficiency；3. MOFs film has cell breath or unsatuated metal site, by right
The selectivity control of hole cage reaction gases concentration ratio is conducive to improve the selectivity of hydrogen peroxide.
In addition to this, by being coated on micro passage reaction inner wall for NMPs-MOFs hybridized film as catalyst, gas is reduced
Liquid consolidates a series of problems, such as entrainment loss of direct mixed system, local channel, short circuit, dead angle, takes full advantage of microchannel plate
The design feature of device and the growth mechanism of NMPs-MOFs hybridized film are answered, the two is organically combined, improves the steady of entire reaction system
Qualitative and life cycle, is conducive to industrialization promotion.
It is worth noting that, NMPs-MOFs hybridized film can regard each interlayer structure unit as one as catalyst
A microreactor realizes quasi- homogeneousization of heterogeneous catalysis, greatly improves catalytic reaction efficiency and product yield.
Because the width of microchannel and height are far below the quenching distance of hydrogen and oxygen free radical in reactor, can
It is limited with breaking hydrogen/oxygen molar ratio by traditional explosion limit, help to improve the selectivity of hydrogen peroxide and strengthens work
The safety of skill operation, significantly improves the safety coefficient of synthesis technology.
Since the active component of load type metal catalyst is easy to happen reunion during the reaction, lead to effective active position
Points drop now, and low so as to cause reaction efficiency, therefore, catalyst is supported in carrier in the synthesizer of the present embodiment
On, but it is wrapped in that large specific surface area, cellular structure are orderly stable, metal containing unsatuated metal site is organic as sandwich
In framework material (MOFs).On the one hand, MOFs can be used as function carrier and wrap up metal nanoparticle (NMPs), realize
Active site high dispersive simultaneously prevents from reuniting, each hole cage can regard a mimicry microreactor as.On the other hand, MOFs can be
The micro-molecular gas such as hydrogen, oxygen are adsorbed and are enriched under the conditions of suitable, improve the part of metal nanoparticle surface
Hydrogen-oxygen concentration, to improve the generating rate of hydrogen peroxide.
Micro passage reaction is a kind of reactor of commercial introduction relative maturity, but according to occurring in micro passage reaction
Reaction is different, and the specific structure of micro passage reaction is also different, and therefore, it is necessary to the structure in channel is designed according to different reactions
With size etc..It is anti-fully considering the present invention is based on the dynamics and thermodynamic behaviour of the reaction of hydrogen-oxygen producing hydrogen peroxide by direct synthesis
On the basis of answering the key factors such as system gas-phase feed, solvent environment, fluid rate and reaction efficiency, to micro passage reaction into
It has gone structure design, that is, has selected suitable channel layout and size.
Illustratively, the present embodiment is fully considering reaction system gas-phase feed, solvent environment, fluid rate and is reacting
On the basis of the key factors such as efficiency, the channel width of feed zone and/or mixed zone is selected as 0.01~0.50mm, channel is deep
Degree is selected as 0.01~0.50mm, and passage length is selected as 50~100mm.This is because when channel width and excessive depth, drop
Low reaction object is effectively contacted with catalyst film, even results in reaction short circuit phenomenon.When passage length is too short, it is catalyzed the reaction time
Deficiency, reaction conversion ratio reduce；When passage length is too long, it is easy to cause excessively catalysis, enhancing side reaction, reduces product yield.
After coating NMPs-MOFs hybridized film in view of the inner wall of substrate and cover plate, inner wall can be thickened, so that microchannel
The inner wall channel narrows of reactor influence the progress of reaction, so, the channel radial dimension of the present embodiment reaction zone is greater than charging
The channel in area and mixed zone.
Specifically, the channel size of catalyst load area (i.e. reaction zone) should guarantee when gas-liquid-solid three-phase mixes
Flow resistance is moderate, guarantees have enough reaction contact times to improve product yield again.Illustratively, the channel of reaction zone
Width is 0.10~1.00mm, and channel depth is 0.10~1.00mm, and passage length is 20~60mm.
For ease of operation, the present invention is not the inner wall that NMPs-MOFs hybridized film is directly coated on to micro passage reaction
On, but using substrate and cover plate as base material, NMPs-MOFs hybridized film is prepared on base material, after the completion of preparation
Using the substrate and cover plate of thermal bonding method assembling micro passage reaction.
In view of local reaction concentration to be improved, need MOFs film that there is good adsorptivity to hydrogen and oxygen, so,
In above-mentioned synthesis technology, the metal center of metal-organic framework materials (MOFs film) is one be selected as in Al, Zr, Cr, Fe, Zn
Kind is a variety of.On the one hand, above-mentioned metal is formed by MOFs film to the excellent adsorption of reactant hydrogen gas and oxygen as skeleton, has
Conducive to the raising of local reaction concentration, and then reaction efficiency is improved, improves product yield；On the other hand, above-mentioned metal is at low cost.
It is worth noting that, the cellular structure of MOFs film is one in MIL, UIO, ZIF in synthesis technology of the invention
Kind.This is because firstly, above-mentioned duct is easier to trapping hydrogen and oxygen, to be more advantageous to the raising of local reaction concentration；
Secondly, the size in above-mentioned duct and the matching degree of metal nanoparticle size are good；Again, above-mentioned pore size and reaction molecular are dynamic
The goodness of fit of aerodynamic diameter size is high.Preferably one of ZIF and MIL.
In view of duct is to the adsorptivity of reactant, that is, hydrogen and oxygen and the peptizaiton of metal active site, this hair
Bright cellular structure specific surface area is 300~3000m2/ g, preferably 800~1500m2/g。
In order to increase reaction efficiency, the present invention selects one of Pt, Pd, Rh, Ru, Au, Ni, Co, Cu and Fe or a variety of
Carry out the reaction of hydrogen catalyzed and oxygen synthesis hydrogen peroxide as metal active site.Above-mentioned metal nanoparticle is to above-mentioned synthesis
The catalytic activity of technique is high, therefore reaction efficiency is high.
When excessive in view of the partial size of metal nanoparticle, the decline of surface effective metal number of active sites, catalytic efficiency
Decline, so, the partial size of metal nanoparticle is not more than 5.0mm in the present invention.Illustratively, partial size is 2.0~5.0nm, excellent
Choosing is 2.0~3.0nm.
When too low in view of metal nanoparticle load capacity, metal active site is very little, it is difficult to meet catalysis reaction needs；
Load capacity is excessively high, and metal nanoparticle size is difficult to control, and catalyst cost will also increase substantially.So the present invention selects
Load capacity is the 0.5%~10.0% of NMPs-MOFs hybridized film gross mass, preferably 1.0~2.5%.
Another embodiment of the invention discloses a kind of preparation method of the NMPs-MOFs hybridized film of sandwich structure:
Include the following steps:
Step 1: being formulated for preparing the precursor solution of metal organic framework and metal salt solution, by the two mixed in equal amounts
Obtain mixed solution；
Step 2: the mixed solution for being used to prepare metal organic framework is passed through into the microchannel of hydrogen peroxide synthesizer,
It is allowed at appropriate temperatures in microchannel interior walls from growing, drying obtains underlying metal organic framework film；
Step 3: being formulated for preparing the metal salt solution of metal nanoparticle；
Step 4: preparing metal nanoparticle with liquid phase reduction and be coated on reaction zone underlying metal organic framework film；
Step 5: continuing to be passed through the mixed solution for preparing metal organic framework into microchannel, be allowed at appropriate temperatures certainly
Growth, coated metal nanoparticles form top-level metallic organic framework film, dry, obtain the NMPs- with sandwich structure
MOFs hybridized film.
Another embodiment of the invention discloses a kind of hydrogen peroxide synthetic method, includes the following steps:
(1) H is passed through into micro passage reaction by two gas feeds and liquid-inlet respectively2、O2And reaction dissolvent；
(2)H2、O2It is mixed in mixed zone with reaction dissolvent；
(3)H2And O2H is synthesized in reaction zone2O2；
(4)H2O2It is exported from product exit.
If being unfavorable for MOFs film pair in view of hydrogen and oxygen are passed directly into micro passage reaction progress synthetic reaction
The absorption and trapping of hydrogen and oxygen are also passed through reaction dissolvent in synthetic method of the invention, it is therefore intended that: first is that by hydrogen and
Oxygen is dissolved in reaction dissolvent, is conducive to MOFs membrane material and is acted on the absorption and trapping of hydrogen and oxygen, to improve metal
The local concentration of active site interfacial reaction, and then improve reaction efficiency；Second is that reaction product is transferred out micro passage reaction.
Specifically, the selection of reaction dissolvent needs to consider following factor: first is that hydrogen and oxygen are molten in the solvent
Solution degree is high；Second is that stability is good in a solvent for hydrogen peroxide reaction product；Third is that the dissolution system of hydrogen and oxygen in the solvent
Number ratio is reasonable.Comprehensively consider above-mentioned factor, reaction dissolvent selected in synthesis technology of the invention is water, C1~C3Alcohol, third
One or more of ketone.Preferably C1~C3One or more of alcohol.
Consider from point of theory, in the reaction of hydrogen and oxygen synthesis hydrogen peroxide, the molar ratio of hydrogen and oxygen is 1:
1, but the influence of the factors such as solubility, structure of micro passage reaction due to the two in reaction dissolvent, O2Flow velocity need
Greater than H2Flow velocity.Experiment discovery, when the velocity ratio of the two is 1:1~4:1, the selectivity of product is good, and product yield is high.Cause
This, O in the present invention2And H2Velocity ratio be selected as 1:1~4:1.Preferably 1.5:1~3:1.
Specifically, the flow velocity of hydrogen and oxygen is 50~300mL/h.This is because when flow velocity is less than 50mL/h, reaction
Residence time is too long, and side reaction influences significant, selectivity of product decline；When flow velocity is greater than 300mL/h, part reactant has little time
Reaction is just flowed out from the outlet of the liquid phase of micro passage reaction, increases the consumption of unnecessary hydrogen and oxygen, to increase
Production cost.Preferably, the flow velocity of hydrogen and oxygen is 80~130mL/h.
Based on same consideration, the flow velocity of reaction dissolvent of the present invention is selected as 0.1~1.0mL/h, preferably 0.3~
0.8mL/h。
It is worth noting that, being unfavorable for reacting effective generation when reaction temperature is low；Reaction temperature is excessively high, product peroxidating
Hydrogen easily decomposes, is unstable, and yield is caused to decline.Therefore, it is 40~120 DEG C that the present invention, which selects reaction temperature, preferably 40~
80 DEG C, more preferably 50~60 DEG C.
Because the present invention can carry out under normal pressure or appropriate pressurized conditions, and reaction pressure is excessively high mentions to reactor design
Requirement out is higher, can increase substantially technological operation cost.So reaction pressure of the invention is selected as 0.1~2.5MPa,
Preferably 0.5~1.0MPa.
Following embodiment chooses representative Pt-Ni as metal nanoparticle, Zn as MOFs material metal center, two
For methylimidazole is ZIF as organic ligand, cellular structure, by metal nanoparticle, the MOFs material metal in embodiment
Center, organic ligand, cellular structure replace with other metal nanoparticles described in the content of present invention, MOFs material metal center,
Organic ligand, cellular structure, the preparation method and condition described using the embodiment of the present invention 1, the NMPs-MOFs hybridized film of preparation
Have the effect of same with embodiment 1.
Embodiment 1
Pt-Ni/ZIF-8 hybridized film is prepared as follows:
Step 1: by Zn (NO3)2(12mmol) and 2-methylimidazole (25mmol) are dissolved in methanol (250mL) and prepare ZIF-8
Precursor solution；
Step 2: by Zn (NO3)2(12mmol) is dissolved in deionized water (250mL) and prepares zinc nitrate aqueous solution；
Step 3: take the ZIF-8 precursor solution of equivalent to be sufficiently mixed with zinc nitrate aqueous solution, it under room temperature will mixing
Solution is passed through in the microchannel formed after substrate and cover plate fastening, and the time for being passed through mixed solution is 80min, and again with methanol is washed
It washs, nitrogen drying, obtains bottom ZIF-8 film；
Step 4: with H2PtCl6With Ni (NO3)2For presoma, Pt is prepared using liquid phase reduction1Ni3Metal nanoparticle,
And pass through spin-coating method for Pt1Ni3Metal nanoparticle is coated on new life ZIF-8 film；
Step 5: continue to be passed through mixed solution into microchannel, it is dry, make to grow top layer in metal nano-particle layer
ZIF-8 film has the Pt-Ni/ZIF-8 hybridized film of sandwich structure to get arriving.
Embodiment 2
Hydrogen-oxygen direct synthesis hydrogen peroxide: the micro- logical of Pt-Ni/ZIF-8 hybridized film will be coated with using thermal bonding method
Road reactor substrate and cover plate are assembled；Liquid inlet is continuously added into methanol solvate with 0.1mL/h flow velocity, hydrogen inlet with
50mL/h is passed through high-purity hydrogen, and oxygen intake is passed through high purity oxygen gas with 50mL/h, and gas and liquid flow through behind mixed zone urges
Change bed region to be reacted, after reaction temperature is 40 DEG C, reaction pressure 0.1MPa, stable reaction 5 hours, hydrogen peroxide is received
Rate is 89%.
Embodiment 3
Hydrogen-oxygen direct synthesis hydrogen peroxide: the micro- logical of Pt-Ni/ZIF-8 hybridized film will be coated with using thermal bonding method
Road reactor substrate and cover plate are assembled；Liquid inlet is continuously added into alcohol solvent with 1.0mL/h flow velocity, hydrogen inlet with
70mL/h is passed through high-purity hydrogen, and oxygen intake is passed through high purity oxygen gas with 280mL/h, and gas and liquid flow through behind mixed zone urges
Change bed region to be reacted, after reaction temperature is 120 DEG C, reaction pressure 2.5MPa, stable reaction 3 hours, hydrogen peroxide
Yield is 91%.
Embodiment 4
Hydrogen-oxygen direct synthesis hydrogen peroxide: the micro- logical of Pt-Ni/ZIF-8 hybridized film will be coated with using thermal bonding method
Road reactor substrate and cover plate are assembled；Liquid inlet is continuously added into methanol solvate with 0.5mL/h flow velocity, hydrogen inlet with
80mL/h is passed through high-purity hydrogen, and oxygen intake is passed through high purity oxygen gas with 160mL/h, and gas and liquid flow through behind mixed zone urges
Change bed region to be reacted, after reaction temperature is 60 DEG C, reaction pressure 1.5MPa, stable reaction 4 hours, hydrogen peroxide is received
Rate is 92%.
Embodiment 5
Hydrogen-oxygen direct synthesis hydrogen peroxide: the micro- logical of Pt-Ni/ZIF-8 hybridized film will be coated with using thermal bonding method
Road reactor substrate and cover plate are assembled；Liquid inlet is continuously added into alcohol solvent with 1.0mL/h flow velocity, hydrogen inlet with
100mL/h is passed through high-purity hydrogen, and oxygen intake is passed through high purity oxygen gas with 150mL/h, and gas and liquid flow through behind mixed zone
Catalytic bed region is reacted, after reaction temperature is 80 DEG C, reaction pressure 2.0MPa, stable reaction 2.5 hours, peroxidating
Hydrogen yield is 94%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of hydrogen peroxide synthesizer, which is characterized in that the synthesizer includes micro passage reaction, including mutually detains
The substrate and cover plate of conjunction, the substrate and the cover plate form microchannel structure after fastening；
The micro passage reaction includes feed zone, mixed zone and reaction zone, the feed zone include gas feed and liquid into
Mouthful, the reaction zone is coated with metal nanoparticle-metal organic framework hybridized film of sandwich structure；The sandwich structure
Are as follows: bottom and top layer are metal organic framework film, and intermediate sandwich of layers is metal nanoparticle.
2. hydrogen peroxide synthesizer according to claim 1, which is characterized in that the channel width of the reaction zone is
0.1~1.0mm, 0.1~1.0mm of channel depth, passage length are 20~60mm.
3. hydrogen peroxide synthesizer according to claim 1, which is characterized in that the feed zone and/or the mixing
The channel width in area is 0.01~0.50mm, and channel depth is 0.01~0.50mm, and passage length is 50~100mm.
4. hydrogen peroxide synthesizer according to claim 1, which is characterized in that in the metal of the metal organic framework
The heart is one of Al, Zr, Cr, Fe, Zn or a variety of.
5. hydrogen peroxide synthesizer according to claim 4, which is characterized in that tie in the duct of the metal organic framework
Structure is one of MIL, UIO, ZIF.
6. hydrogen peroxide synthesizer according to claim 1, which is characterized in that the metal nanoparticle be Pt, Pd,
One of Rh, Ru, Au, Ni, Co, Cu and Fe or a variety of；The load capacity of the metal nanoparticle is metal nanoparticle-gold
Belong to the 0.5%~10.0% of organic backbone hybridized film gross mass.
7. hydrogen peroxide synthesizer according to claim 1, which is characterized in that the quantity of the gas feed is two
It is a.
8. a kind of metal nanoparticle of sandwich structure-metal organic framework hybridized film preparation method: it is characterized in that, packet
Include following steps:
Step 1: being formulated for preparing the precursor solution of metal organic framework and metal salt solution, the two mixed in equal amounts is obtained
Mixed solution；
Step 2: being passed through into the microchannel of hydrogen peroxide synthesizer described in claim 1-7 and be used to prepare the organic bone of metal
The mixed solution of frame, it is dry, obtain underlying metal organic framework film；
Step 3: being formulated for preparing the metal salt solution of metal nanoparticle；
Step 4: preparing metal nanoparticle with liquid phase reduction and be coated on the underlying metal organic framework film of reaction zone；
Step 5: continue to be passed through the mixed solution for preparing metal organic framework into microchannel, coated metal nanoparticles, it is dry,
Top-level metallic organic framework film is formed, the metal nanoparticle with sandwich structure-metal organic framework hybridized film is obtained.
9. a kind of hydrogen peroxide synthetic method, which is characterized in that closed using hydrogen peroxide synthesizer described in claim 1-7
At hydrogen peroxide, include the following steps:
(1) H is passed through into micro passage reaction by two gas feeds and liquid-inlet respectively2、O2And reaction dissolvent；
(2)H2、O2It is mixed in mixed zone with reaction dissolvent；
(3)H2And O2H is synthesized in reaction zone2O2；
(4)H2O2It is exported from product exit.
10. hydrogen peroxide synthetic method according to claim 9, which is characterized in that O2And H2Velocity ratio be 1:1~4:
1, reaction temperature is 40~120 DEG C, and reaction pressure is 0.1~2.5MPa.
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