CN109589890B - Hydrogen peroxide synthesis device and method - Google Patents
Hydrogen peroxide synthesis device and method Download PDFInfo
- Publication number
- CN109589890B CN109589890B CN201910027525.7A CN201910027525A CN109589890B CN 109589890 B CN109589890 B CN 109589890B CN 201910027525 A CN201910027525 A CN 201910027525A CN 109589890 B CN109589890 B CN 109589890B
- Authority
- CN
- China
- Prior art keywords
- metal
- reaction
- hydrogen peroxide
- organic framework
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000003786 synthesis reaction Methods 0.000 title claims description 23
- 230000015572 biosynthetic process Effects 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000012528 membrane Substances 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 239000002082 metal nanoparticle Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 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
- 229910052759 nickel Inorganic materials 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
- 239000001301 oxygen Substances 0.000 abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 43
- 239000001257 hydrogen Substances 0.000 abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 41
- 239000000758 substrate Substances 0.000 abstract description 12
- 238000001308 synthesis method Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004880 explosion Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 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
- 239000002904 solvent Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 8
- 229910002845 Pt–Ni Inorganic materials 0.000 description 7
- 239000000376 reactant Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000012071 phase Substances 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
- 206010024769 Local reaction Diseases 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000000265 homogenisation Methods 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
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and aims to: firstly Substances 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 208000012839 conversion disease Diseases 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B01J35/59—
-
- 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
Abstract
The invention relates to a device and a method for synthesizing hydrogen peroxide, which belong to the technical field of hydrogen peroxide and solve the following problems in the prior art: (1) the mixed explosion range of the hydrogen and oxygen raw materials is wider, and the danger coefficient is high; (2) the solubility of hydrogen and oxygen in a reaction medium is low, so that the reaction efficiency is difficult to meet the requirement of industrial production; (3) in the reaction process, the hydrogen and oxygen are directly generated into water and the hydrogen peroxide is decomposed, and the like, so that the selectivity of the product is low. The microchannel reactor comprises a substrate and a cover plate which are mutually buckled, and a microchannel structure is formed after the substrate and the cover plate are buckled; the microchannel reactor comprises a feeding area, a mixing area and a reaction area, wherein the reaction area is coated with a metal nanoparticle-metal organic framework hybrid membrane with a sandwich structure. The synthesis method of the hydrogen peroxide comprises the following steps: introduction of H2、O2And reaction solvent → H2、O2Mixing with reaction solvent → production of H2O2. The invention realizes the safe, high-quality and high-efficiency production of the hydrogen peroxide.
Description
Technical Field
The invention relates to the technical field of hydrogen peroxide, in particular to a hydrogen peroxide synthesis device and a hydrogen peroxide synthesis method.
Background
The hydrogen peroxide only generates oxygen and water in the using process, is an environment-friendly chemical product, and can be widely applied to the industries of chemical industry, textile, papermaking, food, environmental protection and the like.
At present, the large-scale industrial production of the hydrogen peroxide mostly adopts an anthraquinone method, the method has mature technology and higher safety coefficient, but has the problems of complex process flow, higher device investment, serious environmental pollution and the like. In recent years, novel methods for synthesizing hydrogen peroxide mainly include a hydrogen-oxygen direct synthesis method, a fuel cell method, a plasma method, a supercritical carbon dioxide method, and the like. The method for directly synthesizing hydrogen peroxide from hydrogen and oxygen is based on ideal atom economic reaction, does not generate toxic substances, has the advantages of economy, high efficiency, environmental protection and is put forward for the first time in 1914 so as to be concerned. The most commonly used catalyst for the direct hydrogen-oxygen synthesis method is a supported metal catalyst, and the common metal active components are Pd, Pt, Au and the like. However, the hydrogen-oxygen concentration on the surface of the active component of the supported metal catalyst is limited by the solubility of the gas, so that the reaction rate is slow and the hydrogen peroxide selectivity is low. In addition, the active components of the supported metal catalyst are prone to agglomeration during the reaction process, resulting in a decrease in the number of effective active sites.
The hydrogen peroxide synthesized directly by oxyhydrogen currently faces the following challenges in industrial application: (1) the mixed explosion range of the hydrogen and oxygen raw materials is wider, and the danger coefficient is high; (2) the solubility of hydrogen and oxygen in a reaction medium is low, so that the reaction efficiency is difficult to meet the requirement of industrial production; (3) in the reaction process, the hydrogen and oxygen are directly generated into water and the hydrogen peroxide is decomposed, and the like, so that the selectivity of the product is low.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a hydrogen peroxide synthesis apparatus and method, which can solve at least one of the following technical problems: (1) the mixed explosion range of the hydrogen and oxygen raw materials is wider, and the danger coefficient is high; (2) the solubility of hydrogen and oxygen in a reaction medium is low, so that the reaction efficiency is difficult to meet the requirement of industrial production; (3) in the reaction process, the hydrogen and oxygen are directly generated into water and the hydrogen peroxide is decomposed, and the like, so that the selectivity of the product is low.
The purpose of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides a hydrogen peroxide synthesis device, which comprises a microchannel reactor, a reactor and a reactor, wherein the microchannel reactor comprises a substrate and a cover plate which are mutually buckled, and a microchannel structure is formed after the substrate and the cover plate are buckled;
the microchannel reactor comprises a feeding area, a mixing area and a reaction area, wherein the feeding area comprises a gas inlet and a liquid inlet, and the reaction area is coated with a metal nanoparticle-metal organic framework hybrid membrane with a sandwich structure; the sandwich structure is as follows: the bottom layer and the top layer are metal organic framework films, and the middle sandwich layer is metal nano-particles.
On the basis of the scheme, the invention is further improved as follows:
furthermore, the width of the channel of the reaction zone is 0.1-1.0 mm, the depth of the channel is 0.1-1.0 mm, and the length of the channel is 20-60 mm.
Furthermore, the width of the channel of the feeding area and/or the mixing area is 0.01-0.50 mm, the depth of the channel is 0.01-0.50 mm, and the length of the channel is 50-100 mm.
Further, the metal center of the metal organic framework is one or more of Al, Zr, Cr, Fe and Zn.
Further, the pore structure of the metal organic framework is one of MIL, UIO and ZIF.
Further, the metal nanoparticles are one or more of Pt, Pd, Rh, Ru, Au, Ni, Co, Cu and Fe; the loading capacity of the metal nano particles is 0.5-10.0% of the total mass of the metal nano particles-metal organic framework hybrid membrane.
Further, the number of the gas inlets is two.
On the other hand, the invention also provides a preparation method of the metal nanoparticle-metal organic framework hybrid membrane with the sandwich structure, which comprises the following steps: the method comprises the following steps:
step 1: preparing a precursor solution for preparing a metal organic framework and a metal salt solution, and mixing the precursor solution and the metal salt solution in equal amount to obtain a mixed solution;
step 2: introducing a mixed solution for preparing a metal-organic framework into the micro-channel of the hydrogen peroxide synthesis device as defined in any one of claims 1 to 7, and drying to obtain a bottom metal-organic framework membrane;
and step 3: preparing a metal salt solution for preparing metal nanoparticles;
and 4, step 4: preparing metal nano particles by a liquid phase reduction method and coating the metal nano particles on a bottom metal organic framework film of a reaction area;
and 5: and continuously introducing the mixed solution for preparing the metal organic framework into the microchannel, wrapping the metal nanoparticles, drying to form a top-layer metal organic framework film, and obtaining the metal nanoparticle-metal organic framework hybrid film with the sandwich structure.
In addition, the invention also discloses a hydrogen peroxide synthesis method, which comprises the following steps:
(1) introducing H into the microchannel reactor through two gas inlets and a liquid inlet respectively2、 O2And a reaction solvent;
(2)H2、O2and a reaction solvent in a mixing zone;
(3)H2and O2Synthesis of H in a reaction zone2O2;
(4)H2O2And is output from the product outlet.
Further, O2And H2The flow rate ratio of (A) is 1: 1-4: 1, the reaction temperature is 40-120 ℃, and the reaction pressure is 0.1-2.5 MPa.
The invention has the following beneficial effects:
(1) according to the invention, a metal nanoparticle-metal organic framework (NMPs-MOFs) hybrid membrane is selected as a catalyst, and the NMPs-MOFs hybrid membrane is designed to be of a sandwich structure, namely, the bottom layer is a Metal Organic Framework (MOFs) membrane, the middle sandwich layer is metal Nanoparticles (NMPs), namely active sites of the catalyst, and the top layer is a MOFs membrane, so that the dispersity of the metal active sites of the NMPs can be effectively improved, and the catalytic activity of a single site is increased; the MOFs film can adsorb and enrich reaction gases, namely hydrogen and oxygen, according to a certain proportion, so that the local concentration of reactants on the surface of the metal active sites of the NMPs is improved, and the reaction efficiency is improved; and thirdly, the MOFs membrane has a breathing effect or unsaturated metal sites, and the selectivity of hydrogen peroxide is favorably improved by selectively controlling the concentration ratio of the reaction gas in the pore cage.
(2) The NMPs-MOFs hybrid membrane is used as a catalyst, each sandwich structure unit can be regarded as a micro-reactor, quasi-homogenization of the heterogeneous catalyst is realized, and the reaction catalysis efficiency is greatly improved.
(3) The invention adopts the microchannel reactor and is based on the dynamics and thermodynamic characteristics of the reaction for directly synthesizing the hydrogen peroxide by the oxyhydrogen, carries out structural design on the microchannel reactor on the basis of fully considering key factors such as gas phase feeding, solvent environment, fluid velocity, reaction efficiency and the like of a reaction system, and improves the reaction efficiency by selecting proper channel width, depth and length.
(4) The NMPs-MOFs hybrid membrane is used as a catalyst to be coated on the inner wall of the microchannel reactor, so that a series of problems of entrainment loss, local channeling, short circuit, dead corners and the like of a gas-liquid-solid direct mixing system are reduced, the structural characteristics of the microchannel reactor and the growth mechanism of the NMPs-MOFs hybrid membrane are fully utilized, the NMPs-MOFs hybrid membrane and the microchannel reactor are organically combined, the stability and the service life cycle of the whole reaction system are improved, and the industrial popularization is facilitated.
(5) The width and depth of the micro-channel in the reactor are far lower than the quenching distance of the hydrogen and oxygen free radicals, so that the limitation of the hydrogen/oxygen molar ratio by the traditional explosion limit can be broken, the selectivity of the hydrogen peroxide is improved, the safety of the process operation is enhanced, and the safety factor of the synthesis process is obviously improved.
(6) The microchannel reactor is light and portable, can be operated in parallel, can be installed in a place required by a customer on line, avoids danger in the process of transporting hydrogen peroxide, and reduces cost.
(7) The synthesis method has the advantages of high atom economy, high operation safety coefficient, high reaction efficiency, high hydrogen peroxide quality, high product yield and the like.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic structural diagram of a microchannel reactor used in an embodiment of the invention.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
The invention discloses a micro-channel reactor, which comprises a base plate and a cover plate which are mutually buckled, wherein the base plate and the cover plate are buckled to form a micro-channel structure.
The microchannel reactor comprises a feeding area, a mixing area and a reaction area, wherein the feeding area comprises 2 gas inlets and 1 liquid inlet, and the reaction area is coated with an NMPs-MOFs hybrid membrane with a sandwich structure; the sandwich structure is as follows: the bottom layer and the top layer are MOFs films, and the middle sandwich layer is NMPs.
Compared with the prior art, the microchannel reactor obviously improves the reaction efficiency, the product yield and the safety coefficient of the synthesis process, and is beneficial to industrial popularization.
Specifically, in the embodiment, an NMPs-MOFs hybrid membrane is selected as a catalyst, and the NMPs-MOFs hybrid membrane is designed to be a sandwich structure, that is, the bottom layer is an MOFs membrane, the middle sandwich is NMPs, that is, an active site of the catalyst, and the top layer is an MOFs membrane, so that firstly, the dispersity of metal active sites of the NMPs can be effectively improved, and the catalytic activity of a single site can be increased; the MOFs film can adsorb and enrich reaction gases, namely hydrogen and oxygen, according to a certain proportion, so that the local concentration of reactants on the surface of the metal active sites of the NMPs is improved, and the reaction efficiency is improved; and thirdly, the MOFs membrane has a breathing effect or unsaturated metal sites, and the selectivity of hydrogen peroxide is favorably improved by selectively controlling the concentration ratio of the reaction gas in the pore cage.
In addition, the NMPs-MOFs hybrid membrane is used as a catalyst to be coated on the inner wall of the microchannel reactor, so that a series of problems of entrainment loss, local channeling, short circuit, dead corners and the like of a gas-liquid-solid direct mixing system are reduced, the structural characteristics of the microchannel reactor and the growth mechanism of the NMPs-MOFs hybrid membrane are fully utilized, the two are organically combined, the stability and the service life cycle of the whole reaction system are improved, and the industrial popularization is facilitated.
It is worth noting that the NMPs-MOFs hybrid membrane is used as a catalyst, each sandwich structure unit can be regarded as a micro-reactor, quasi-homogenization of the heterogeneous catalyst is realized, and the reaction catalysis efficiency and the product yield are greatly improved.
Because the width and height of the microchannel in the reactor are far lower than the quenching distance of the hydrogen and oxygen free radicals, the limitation of the hydrogen/oxygen molar ratio by the traditional explosion limit can be broken, the selectivity of the hydrogen peroxide is improved, the safety of the process operation is enhanced, and the safety factor of the synthesis process is obviously improved.
Because the active components of the supported metal catalyst are easy to agglomerate in the reaction process, the number of effective active sites is reduced, and the reaction efficiency is low, the catalyst in the synthesis device of the embodiment is not supported on a carrier, but is wrapped in metal organic framework Materials (MOFs) which have large specific surface area, ordered and stable pore channel structure and contain unsaturated metal sites as a sandwich. On one hand, MOFs can be used as a functional carrier to wrap metal Nanoparticles (NMPs), so that high dispersion of active sites is realized, agglomeration is prevented, and each hole cage can be used as a mimicry microreactor. On the other hand, the MOFs can adsorb and enrich hydrogen, oxygen and other small molecule gases under appropriate conditions, and increase the local hydrogen-oxygen concentration on the surface of the metal nanoparticles, thereby increasing the generation rate of hydrogen peroxide.
The microchannel reactor is a type of reactor which is relatively mature in industrial popularization, but the specific structure of the microchannel reactor is different according to different reactions occurring in the microchannel reactor, so that the structure, the size and the like of a channel need to be designed according to different reactions. The invention is based on the dynamics and thermodynamic characteristics of the reaction for directly synthesizing hydrogen peroxide by oxyhydrogen, and carries out structural design on the microchannel reactor on the basis of fully considering key factors such as gas phase feeding of a reaction system, solvent environment, fluid rate, reaction efficiency and the like, namely, selecting proper channel layout and size.
Illustratively, in this embodiment, on the basis of fully considering key factors such as gas-phase feeding, solvent environment, fluid velocity and reaction efficiency of the reaction system, the channel width of the feeding zone and/or the mixing zone is selected to be 0.01-0.50 mm, the channel depth is selected to be 0.01-0.50 mm, and the channel length is selected to be 50-100 mm. This is because, when the channel width and depth are too large, the effective contact of the reactant with the catalyst film is reduced, and even a reaction short-circuit phenomenon is caused. When the length of the channel is too short, the catalytic reaction time is insufficient, and the reaction conversion rate is reduced; when the length of the channel is too long, excessive catalysis is easily caused, side reactions are enhanced, and the yield of products is reduced.
Considering that the inner walls of the substrate and the cover plate can be thickened after being coated with the NMPs-MOFs hybrid membrane, so that the channels of the inner walls of the microchannel reactor are narrowed, and the reaction is influenced, the radial dimension of the channels in the reaction zone is larger than the channels in the feeding zone and the mixing zone.
Specifically, the size of the channels in the catalyst loading zone (i.e., the reaction zone) is such that the flow resistance of the fluid is moderate when the three phases gas, liquid and solid are mixed, and sufficient reaction contact time is ensured to increase the product yield. Illustratively, the width of the channel in the reaction zone is 0.10-1.00 mm, the depth of the channel is 0.10-1.00 mm, and the length of the channel is 20-60 mm.
In order to facilitate the operation, the invention does not directly coat the NMPs-MOFs hybrid membrane on the inner wall of the microchannel reactor, but takes a substrate and a cover plate as base materials, prepares the NMPs-MOFs hybrid membrane on the base materials, and adopts a thermal bonding method to assemble the substrate and the cover plate of the microchannel reactor after the preparation is finished.
In view of the requirement of improving the local reaction concentration, the MOFs film needs to have good adsorptivity to hydrogen and oxygen, so in the above synthesis process, the metal center of the metal organic framework material (MOFs film) is selected to be one or more of Al, Zr, Cr, Fe, Zn. On one hand, the MOFs film formed by the metal as the framework has good adsorbability on reactant hydrogen and oxygen, and is beneficial to improving local reaction concentration, so that the reaction efficiency is improved, and the product yield is improved; on the other hand, the metal is low in cost.
It is worth noting that in the synthesis process of the present invention, the pore structure of the MOFs film is one of MIL, UIO, ZIF. This is because, first, the above-mentioned channels trap hydrogen and oxygen more easily, and thus contribute more to the increase of the local reaction concentration; secondly, the size of the pore channel is well matched with the size of the metal nano-particles; thirdly, the goodness of fit between the pore size and the kinetic diameter size of the reaction molecules is high. Preferably one of ZIF and MIL.
Considering the adsorbability of the pore to reactants, namely hydrogen and oxygen, and the dispersion effect of metal active sites, the specific surface area of the pore structure is 300-3000 m2A preferred concentration is 800 to 1500m2/g。
In order to increase the reaction efficiency, one or more of Pt, Pd, Rh, Ru, Au, Ni, Co, Cu and Fe are selected as metal active sites to catalyze the reaction of synthesizing hydrogen peroxide from hydrogen and oxygen. The metal nanoparticles have high catalytic activity for the synthesis process, and thus have high reaction efficiency.
Considering that the number of surface-effective metal active sites is decreased and the catalytic efficiency is decreased when the particle size of the metal nanoparticles is excessively large, the particle size of the metal nanoparticles in the present invention is not more than 5.0 mm. Illustratively, the particle size is 2.0 to 5.0nm, preferably 2.0 to 3.0 nm.
Considering that when the loading capacity of the metal nano particles is too low, the metal active sites are too few, and the requirement of catalytic reaction is difficult to meet; the loading capacity is too high, the size of the metal nano particles is difficult to control, and the cost of the catalyst is greatly improved. Therefore, the selective loading capacity of the invention is 0.5-10.0% of the total mass of the NMPs-MOFs hybrid membrane, and preferably 1.0-2.5%.
The other embodiment of the invention discloses a preparation method of the NMPs-MOFs hybrid membrane with the sandwich structure, which comprises the following steps: the method comprises the following steps:
step 1: preparing a precursor solution for preparing a metal organic framework and a metal salt solution, and mixing the precursor solution and the metal salt solution in equal amount to obtain a mixed solution;
step 2: introducing a mixed solution for preparing a metal organic framework into a micro-channel of a hydrogen peroxide synthesis device, enabling the mixed solution to grow on the inner wall of the micro-channel at a proper temperature, and drying to obtain a bottom layer metal organic framework film;
and step 3: preparing a metal salt solution for preparing metal nanoparticles;
and 4, step 4: preparing metal nano particles by a liquid phase reduction method and coating the metal nano particles on a metal organic framework film at the bottom layer of a reaction zone;
and 5: and continuously introducing the mixed solution for preparing the metal organic framework into the microchannel, enabling the mixed solution to grow at a proper temperature, wrapping metal nano particles to form a top metal organic framework film, and drying to obtain the NMPs-MOFs hybrid film with the sandwich structure.
Another embodiment of the invention discloses a method for synthesizing hydrogen peroxide, which comprises the following steps:
(1) introducing H into the microchannel reactor through two gas inlets and a liquid inlet respectively2、 O2And a reaction solvent;
(2)H2、O2and a reaction solvent in a mixing zone;
(3)H2and O2Synthesis of H in a reaction zone2O2;
(4)H2O2And is output from the product outlet.
Considering that if the synthesis reaction of hydrogen and oxygen directly introduced into the microchannel reactor is not beneficial to the adsorption and trapping of the hydrogen and oxygen by the MOFs membrane, the synthesis method of the invention also introduces a reaction solvent, and aims to: firstly, hydrogen and oxygen are dissolved in a reaction solvent, which is beneficial to the adsorption and trapping effects of MOFs membrane materials on the hydrogen and the oxygen, so that the local concentration of the interface reaction of metal active sites is improved, and the reaction efficiency is further improved; and secondly, conveying the reaction product out of the microchannel reactor.
In particular, the choice of reaction solvent requiresThe following factors are considered: firstly, the solubility of hydrogen and oxygen in the solvent is high; secondly, the reaction product hydrogen peroxide has good stability in a solvent; thirdly, the dissolution coefficient proportion of the hydrogen and the oxygen in the solvent is reasonable. Taking the above factors into consideration, the reaction solvents selected in the synthesis process of the invention are water and C1~C3One or more of alcohol and acetone. Preferably C1~C3One or more of alcohols.
From the theoretical point of view, in the reaction for synthesizing hydrogen peroxide by hydrogen and oxygen, the molar ratio of the hydrogen to the oxygen is 1:1, but O is influenced by factors such as the solubility of the hydrogen and the oxygen in a reaction solvent, the structure of a microchannel reactor and the like2The flow rate of (A) needs to be greater than H2The flow rate of (c). Experiments show that when the flow rate ratio of the two is 1: 1-4: 1, the selectivity of the product is good, and the product yield is high. Thus, O in the present invention2And H2The flow rate ratio of (A) is selected to be 1:1 to 4: 1. Preferably 1.5:1 to 3: 1.
Specifically, the flow rate of the hydrogen and the oxygen is 50-300 mL/h. This is because, when the flow rate is less than 50mL/h, the reaction residence time is too long, the side reaction effect is significant, and the product selectivity is reduced; when the flow rate is more than 300mL/h, part of reactants flow out of a gas-liquid phase outlet of the microchannel reactor before reaction, and unnecessary consumption of hydrogen and oxygen is increased, so that the production cost is increased. Preferably, the flow rate of the hydrogen and the oxygen is 80-130 mL/h.
In the same sense, the flow rate of the reaction solvent of the present invention is selected to be 0.1 to 1.0mL/h, preferably 0.3 to 0.8 mL/h.
It is worth noting that when the reaction temperature is low, the reaction is not favorable to occur effectively; the reaction temperature is too high, and the product hydrogen peroxide is easy to decompose and unstable, so that the yield is reduced. Therefore, the reaction temperature is selected to be 40-120 ℃, preferably 40-80 ℃, and more preferably 50-60 ℃.
The invention can be carried out under normal pressure or proper pressurization, and the higher reaction pressure puts higher requirements on the design of the reactor, thereby greatly improving the process operation cost. Therefore, the reaction pressure in the present invention is selected to be 0.1 to 2.5MPa, preferably 0.5 to 1.0 MPa.
In the following embodiment, representative Pt-Ni is selected as a metal nanoparticle, Zn is selected as a metal center of a MOFs material, dimethylimidazole is used as an organic ligand, and a pore structure is ZIF, and the metal nanoparticle, the metal center of the MOFs material, the organic ligand, and the pore structure in the embodiment are replaced with other metal nanoparticles, metal centers of the MOFs material, organic ligands, and pore structures described in the disclosure of the present invention, and the NMPs-MOFs hybrid film prepared by using the preparation method and conditions described in embodiment 1 of the present invention has the same effect as that in embodiment 1.
Example 1
The Pt-Ni/ZIF-8 hybrid membrane is prepared by the following method:
step 1: adding Zn (NO)3)2Dissolving (12mmol) and 2-methylimidazole (25mmol) in methanol (250mL) to prepare a ZIF-8 precursor solution;
step 2: adding Zn (NO)3)2(12mmol) is dissolved in deionized water (250mL) to prepare zinc nitrate aqueous solution;
and step 3: taking an equal amount of ZIF-8 precursor solution and a zinc nitrate aqueous solution, fully mixing, introducing the mixed solution into a micro-channel formed by buckling a substrate and a cover plate at room temperature, introducing the mixed solution for 80min, washing with methanol, and drying with nitrogen to obtain a bottom ZIF-8 film;
and 4, step 4: with H2PtCl6And Ni (NO)3)2Preparing Pt by liquid phase reduction method as precursor1Ni3Metal nanoparticles, and Pt by spin coating1Ni3Coating metal nanoparticles on the nascent ZIF-8 membrane;
and 5: and continuously introducing the mixed solution into the microchannel, and drying to grow a top ZIF-8 film on the metal nanoparticle layer, thereby obtaining the Pt-Ni/ZIF-8 hybrid film with the sandwich structure.
Example 2
Hydrogen peroxide is synthesized by an oxyhydrogen direct method: assembling the substrate and the cover plate of the micro-channel reactor coated with the Pt-Ni/ZIF-8 hybrid membrane by adopting a thermal bonding method; the methanol solvent is continuously added into the liquid inlet at the flow rate of 0.1mL/h, the high-purity hydrogen is introduced into the hydrogen inlet at the flow rate of 50mL/h, the high-purity oxygen is introduced into the oxygen inlet at the flow rate of 50mL/h, the gas and the liquid flow through the area of the catalytic bed after passing through the mixing area to react, the reaction temperature is 40 ℃, the reaction pressure is 0.1MPa, and the yield of the hydrogen peroxide is 89% after the reaction is stable for 5 hours.
Example 3
Hydrogen peroxide is synthesized by an oxyhydrogen direct method: assembling the substrate and the cover plate of the micro-channel reactor coated with the Pt-Ni/ZIF-8 hybrid membrane by adopting a thermal bonding method; the ethanol solvent is continuously added into the liquid inlet at the flow rate of 1.0mL/h, the high-purity hydrogen is introduced into the hydrogen inlet at the flow rate of 70mL/h, the high-purity oxygen is introduced into the oxygen inlet at the flow rate of 280 mL/h, the gas and the liquid flow through the catalytic bed area after passing through the mixing area to react, the reaction temperature is 120 ℃, the reaction pressure is 2.5MPa, and the yield of the hydrogen peroxide is 91% after the reaction is stable for 3 hours.
Example 4
Hydrogen peroxide is synthesized by an oxyhydrogen direct method: assembling the substrate and the cover plate of the micro-channel reactor coated with the Pt-Ni/ZIF-8 hybrid membrane by adopting a thermal bonding method; the methanol solvent is continuously added into the liquid inlet at the flow rate of 0.5mL/h, the high-purity hydrogen is introduced into the hydrogen inlet at the flow rate of 80mL/h, the high-purity oxygen is introduced into the oxygen inlet at the flow rate of 160 mL/h, the gas and the liquid flow through the area of the catalytic bed after passing through the mixing area to react, the reaction temperature is 60 ℃, the reaction pressure is 1.5MPa, and the yield of the hydrogen peroxide is 92% after the reaction is stable for 4 hours.
Example 5
Hydrogen peroxide is synthesized by an oxyhydrogen direct method: assembling the substrate and the cover plate of the micro-channel reactor coated with the Pt-Ni/ZIF-8 hybrid membrane by adopting a thermal bonding method; the ethanol solvent is continuously added into the liquid inlet at the flow rate of 1.0mL/h, the high-purity hydrogen is introduced into the hydrogen inlet at the flow rate of 100mL/h, the high-purity oxygen is introduced into the oxygen inlet at the flow rate of 150 mL/h, the gas and the liquid flow through the catalytic bed area after passing through the mixing area to react, the reaction temperature is 80 ℃, the reaction pressure is 2.0MPa, and the yield of the hydrogen peroxide is 94% after the reaction is stable for 2.5 hours.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (8)
1. A hydrogen peroxide synthesizer is characterized by comprising a microchannel reactor, a reactor body and a reactor cover, wherein the microchannel reactor comprises a base plate and a cover plate which are mutually buckled, and a microchannel structure is formed after the base plate and the cover plate are buckled;
the microchannel reactor comprises a feeding area, a mixing area and a reaction area, wherein the feeding area comprises a gas inlet and a liquid inlet, and the reaction area is coated with a metal nanoparticle-metal organic framework hybrid membrane with a sandwich structure; the sandwich structure is as follows: the bottom layer and the top layer are metal organic framework films, and the middle sandwich layer is metal nano-particles;
the width of a channel of the reaction zone is 0.1-1.0 mm, the depth of the channel is 0.1-1.0 mm, and the length of the channel is 20-60 mm;
the width of the channel of the feeding area and/or the mixing area is 0.01-0.50 mm, the depth of the channel is 0.01-0.50 mm, and the length of the channel is 50-100 mm.
2. The apparatus for synthesizing hydrogen peroxide according to claim 1, wherein the metal center of the metal-organic framework is one or more of Al, Zr, Cr, Fe and Zn.
3. The apparatus for synthesizing hydrogen peroxide according to claim 2, wherein the pore structure of the metal-organic framework is one of MIL, UIO and ZIF.
4. The hydrogen peroxide synthesis apparatus according to claim 1, wherein the metal nanoparticles are one or more of Pt, Pd, Rh, Ru, Au, Ni, Co, Cu and Fe; the loading capacity of the metal nano particles is 0.5-10.0% of the total mass of the metal nano particles-metal organic framework hybrid membrane.
5. The hydrogen peroxide synthesis apparatus according to claim 1, wherein the number of the gas inlets is two.
6. A preparation method of a metal nanoparticle-metal organic framework hybrid membrane with a sandwich structure comprises the following steps: the method is characterized by comprising the following steps:
step 1: preparing a precursor solution for preparing a metal organic framework and a metal salt solution, and mixing the precursor solution and the metal salt solution in equal amount to obtain a mixed solution;
step 2: introducing a mixed solution for preparing a metal-organic framework into the micro-channel of the hydrogen peroxide synthesis device as defined in any one of claims 1 to 5, and drying to obtain a bottom metal-organic framework membrane;
and step 3: preparing a metal salt solution for preparing metal nanoparticles;
and 4, step 4: preparing metal nano particles by a liquid phase reduction method and coating the metal nano particles on a bottom metal organic framework film of a reaction area;
and 5: and continuously introducing the mixed solution for preparing the metal organic framework into the microchannel, wrapping the metal nanoparticles, drying to form a top-layer metal organic framework film, and obtaining the metal nanoparticle-metal organic framework hybrid film with the sandwich structure.
7. A method for synthesizing hydrogen peroxide by using the apparatus for synthesizing hydrogen peroxide according to any one of claims 1 to 5, comprising the steps of:
(1) introducing H into the microchannel reactor through two gas inlets and a liquid inlet respectively2、O2And a reaction solvent;
(2)H2、O2and a reaction solvent in a mixing zone;
(3)H2and O2Synthesis of H in a reaction zone2O2;
(4)H2O2And is output from the product outlet.
8. The process for the synthesis of hydrogen peroxide according to claim 7, which comprisesCharacterized in that O2And H2The flow rate ratio of (A) is 1: 1-4: 1, the reaction temperature is 40-120 ℃, and the reaction pressure is 0.1-2.5 MPa.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910027525.7A CN109589890B (en) | 2019-01-11 | 2019-01-11 | Hydrogen peroxide synthesis device and method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910027525.7A CN109589890B (en) | 2019-01-11 | 2019-01-11 | Hydrogen peroxide synthesis device and method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109589890A CN109589890A (en) | 2019-04-09 |
CN109589890B true CN109589890B (en) | 2021-02-26 |
Family
ID=65966174
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910027525.7A Active CN109589890B (en) | 2019-01-11 | 2019-01-11 | Hydrogen peroxide synthesis device and method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109589890B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111203279B (en) * | 2020-02-06 | 2023-04-25 | 安徽大学 | Sandwich nano material ZIF-8@Au 25 @ ZIF-67 and preparation method and application thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102836675B (en) * | 2006-03-23 | 2016-06-15 | 万罗赛斯公司 | A kind of device |
CN103182278A (en) * | 2012-01-03 | 2013-07-03 | 博瑞生物医药技术(苏州)有限公司 | Membrane dispersion type microchannel reactor |
CN102993221B (en) * | 2012-12-13 | 2015-04-22 | 江南大学 | Method for preparing nano-zeolite metal-organic framework compounds by microreactor |
CN105170049B (en) * | 2015-09-11 | 2019-05-28 | 中国石油化工股份有限公司 | The method for preparing hydrogen peroxide using micro passage reaction |
US10847807B2 (en) * | 2016-11-16 | 2020-11-24 | The Trustees Of The Stevens Institute Of Technology | Flexible, planar, double sided air breathing microscale fuel cell |
CN106823854A (en) * | 2017-02-28 | 2017-06-13 | 北京工业大学 | A kind of preparation method of polymer-based metal organic backbone hybridized film |
CN106914200B (en) * | 2017-03-06 | 2019-07-16 | 大连理工大学 | A kind of capillary type load palladium zirconium-based metallic organic framework film microreactor, dynamic in-situ preparation method and applications |
-
2019
- 2019-01-11 CN CN201910027525.7A patent/CN109589890B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN109589890A (en) | 2019-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wei et al. | Recent advance in single-atom catalysis | |
Luo et al. | Anchoring IrPdAu nanoparticles on NH2-SBA-15 for fast hydrogen production from formic acid at room temperature | |
Liu et al. | Metal or metal-containing nanoparticle@ MOF nanocomposites as a promising type of photocatalyst | |
Liu et al. | The development of MOFs-based nanomaterials in heterogeneous organocatalysis | |
Wang et al. | The recent development of efficient Earth-abundant transition-metal nanocatalysts | |
Bi et al. | Efficient degradation of toluene over ultra-low Pd supported on UiO-66 and its functional materials: Reaction mechanism, water-resistance, and influence of SO2 | |
Liu et al. | Applications of metal–organic framework composites in CO2 capture and conversion | |
Xu et al. | Thermocatalytic formic acid dehydrogenation: recent advances and emerging trends | |
Guo et al. | A minireview on the synthesis of single atom catalysts | |
Farajzadeh et al. | Anchoring Pd-nanoparticles on dithiocarbamate-functionalized SBA-15 for hydrogen generation from formic acid | |
Park et al. | A highly active and stable palladium catalyst on a gC 3 N 4 support for direct formic acid synthesis under neutral conditions | |
Olajire | Recent progress on the nanoparticles-assisted greenhouse carbon dioxide conversion processes | |
Verma et al. | Recent strategies for enhancing the catalytic activity of CO2 hydrogenation to formate/formic acid over Pd-based catalyst | |
Jin et al. | Effect of the amine group content on catalytic activity and stability of mesoporous silica supported Pd catalysts for additive-free formic acid dehydrogenation at room temperature | |
Issa Hamoud et al. | Selective photocatalytic dehydrogenation of formic acid by an in situ-restructured copper-postmetalated metal–organic framework under visible light | |
Kouhdareh et al. | Immobilization of Ag and Pd over a novel amide based covalent organic framework (COF-BASU2) as a heterogeneous reusable catalyst to reduce nitroarenes | |
Liu et al. | Enhanced photocatalytic CO2 reduction by integrating an iron based metal-organic framework and a photosensitizer | |
Liu et al. | Toward green production of chewing gum and diet: complete hydrogenation of xylose to xylitol over ruthenium composite catalysts under mild conditions | |
Jafarpour et al. | Tandem photocatalysis protocol for hydrogen generation/olefin hydrogenation using Pd-g-C3N4-Imine/TiO2 nanoparticles | |
CN109589890B (en) | Hydrogen peroxide synthesis device and method | |
Lu et al. | Direct and efficient synthesis of clean H2O2 from CO-assisted aqueous O2 reduction | |
Demirci | Exploring the technological maturity of hydrogen production by hydrolysis of sodium borohydride | |
Pan et al. | Spatial compartmentalization of metal nanoparticles within metal-organic frameworks for tandem reaction | |
He et al. | Sulfur defect induced Cd0. 3Zn0. 7S in-situ anchoring on metal organic framework for enhanced photothermal catalytic CO2 reduction to prepare proportionally adjustable syngas | |
Song et al. | Cobalt phthalocyanine supported on mesoporous CeO2 as an active molecular catalyst for CO oxidation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |