CN109208025A - A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor - Google Patents

A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor Download PDF

Info

Publication number
CN109208025A
CN109208025A CN201710517827.3A CN201710517827A CN109208025A CN 109208025 A CN109208025 A CN 109208025A CN 201710517827 A CN201710517827 A CN 201710517827A CN 109208025 A CN109208025 A CN 109208025A
Authority
CN
China
Prior art keywords
reactor
amorphous alloy
insert
based amorphous
catalytic reactor
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.)
Pending
Application number
CN201710517827.3A
Other languages
Chinese (zh)
Inventor
刘志红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201710517827.3A priority Critical patent/CN109208025A/en
Publication of CN109208025A publication Critical patent/CN109208025A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/40—Cells or assemblies of cells comprising electrodes made of particles; Assemblies of constructional parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

A kind of Fe-based amorphous alloy catalytic reactor is made of reactor frame and draw and insert-type catalytic reactor, reactor frame section configuration can be the structures such as groove profile, U-shaped, draw and insert-type catalytic reactor is made of the sheet-like particle of metal mesh cladding Fe-based amorphous alloy, the specific ingredient of sheet-like particle is Fe35-95 wt%, remaining alloying element be can together with iron one of element, such as P, Co, Ni, Cr, Mo, W, Re of electro-deposition or multiple element combination.The production method of reactor, comprising the following steps: (1) preparation process of draw and insert-type catalytic reactor；(2) sheet metal or polymer are used, reactor frame is made；(3) draw and insert-type catalytic reactor is placed in two fixed plates of reactor frame, Fe-based amorphous alloy catalytic reactor is made.

Description

A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor
Technical field
The present invention relates to the catalytic reactors of electrochemical field, are related specifically to a kind of Fe-based amorphous alloy catalysis reaction The manufacturing method of device.
Background technique
Amorphous alloy is due to having the characteristics that；1. various compositions can be made in amorphous alloy in a wide range Sample, so as to their electronic property of modulation in compared with broad range；2. catalytic active center can be in single form It is evenly distributed in the environment of chemical homogeneous；3. amorphous alloy surface has the higher unsaturated center of concentration, and unsaturated The ligancy at center has certain range, thus its catalytic activity and selectivity is made to be generally preferred over corresponding crystalline-state catalyst； 4. the imporosity on its surface is the problem of its surface that extends influence for getting rid of reaction species existing for multinomial catalyst is reacted.
Amorphous alloy catalyst can be used for plus the reactions such as hydrogen, oxidation, cracking, isomerization.Currently, amorphous alloy is urged There are many preparation methods of agent, in general can be classified as two major classes: liquid is quenched method and atom (ion) sedimentation. Amorphous alloy catalysis electrode is based on the two-dimentional catalysis electrode of deposition film or coating, but its reactor areas is smaller, causes to produce Rate is smaller.
Summary of the invention
In view of the above problems, the present invention proposes a kind of manufacturing method of Fe-based amorphous alloy catalytic reactor.Of the invention Technical solution is to provide a kind of Fe-based amorphous alloy catalytic reactor, which is characterized in that reactor is by reactor frame and pumping Formula catalytic reactor composition is inserted, reactor frame section configuration can be the structures such as groove profile, U-shaped, and draw and insert-type catalytic reactor is by metal The sheet-like particle of net cladding Fe-based amorphous alloy is made, and the specific ingredient of sheet-like particle is Fe35-95 wt %, remaining alloy member Element for can together with iron one of element, such as P, Co, Ni, Cr, Mo, W, Re of electro-deposition or multiple element combination.Instead It answers device frame by sheet metal or polymer preparation molding, is uniformly provided with slot and fixation in the both side plate of reactor frame Plate.
The technical solution of the invention is as follows provides a kind of manufacturing method of Fe-based amorphous alloy catalytic reactor again, including Following steps:
(1) preparation process of draw and insert-type catalytic reactor
1) production of ferrous alloy amorphous deposit
(a) metal substrate is plated the degreasing and oxidation film removal on surface, and metal substrate material should be suitable for the plasticity carried out under room temperature Processing；
(b) electroplate liquid forms；Main salt is soluble ferrite 0.5-4.5mol/L, sour 0.2-0.8mol/L, complexing agent 0.5-5g/ L, alloying element additive 0.2-4mol/L, reducing agent 0.5-4g/L, water surplus；
In the upper alloying element additive, nickel with soluble nickel salt, cobalt with cobaltous sulfate, chromium with chromic anhydride, molybdenum with sodium molybdate, tungsten with Sodium tungstate, phosphorus are added in the form of Re soluble salt by phosphorous acid or soluble hypophosphites, Re；
Above-mentioned acid includes the polynary middle strong acid such as boric acid, phosphoric acid；
Above-mentioned complexing agent includes the organic complexing agents such as neopelex, tartaric acid, citrate；
(c) Fe-based amorphous alloy coating is prepared using plating or Brush Plating, anode uses graphite or stainless steel, and electrolyte temperature is 40-90 DEG C, titration strong acid solution makes Ph value no more than 2；
2) removing of amorphous alloy coating
Using method mechanically or physically, such as the methods of stretching, bending, rolling reductions, scraping makes amorphous alloy coating and metal Substrate is peeling-off；
3) particle is broken
(a) it using ball mill, planetary ball mill etc., is recycled using ball milling (3-10min), this interval of stalling (3-10min) Mode, or can be added simultaneously using ball milling and force cooling ball milling method, amorphous particle is under the conditions of vacuum or protective gas Ball milling is carried out, ball milling total time (time comprising ball milling and stalling) is 0.5-3h, ratio of grinding media to material 2-8:1；
(b) it is sieved into the Fe-based amorphous alloy particle of different thicknesses；
4) can draw and insert-type catalytic reactor metallic cover net molding
Using metal mesh, cut, bending, soldering preparation cladding metal mesh,
5) injection and encapsulation of Amorphous Alloy Grain
Fe-based amorphous alloy particle is injected into cladding metal mesh, then closes cladding metal mesh using modes such as solderings.
(2) preparation process of reactor frame
Using sheet metal or polymer, reactor frame is prepared.
(3) it is assembled into Fe-based amorphous alloy catalysis electrode
Draw and insert-type catalytic reactor is placed in two fixed plates of reactor frame, Fe-based amorphous alloy catalytic reactor is made.
Compared with prior art, advantages of the present invention:
1. due to, as catalyst, catalytic performance can be improved using Fe-based amorphous alloy particle；
2. particle basic configuration is lamellar, this raising due to preparing Fe-based amorphous alloy particle using plating+removing+broken The surface area of amorphous alloy catalyst reaction；
3. due to using reactor frame, can there are enough spacing between draw and insert-type catalytic reactor, and offered in both side plate Slot, end is also unclosed, improves reaction solution or gas to greatest extent in the flowability of inside reactor, increases Relative flow between reactor and reaction solution and gas, can be improved catalytic efficiency；
4. reactor areas and spacing are easily achieved adjustment due to using draw and insert-type structure, it is also convenient for replacement and dimension It repairs.
Detailed description of the invention
Fig. 1 is present device schematic diagram.Wherein, reactor frame (1), can be used sheet metal or polymer is made；It takes out It inserts formula catalytic reactor (2), is made of metal mesh cladding Fe-based amorphous alloy particle；Fixed plate (3)；Slot (4).
Specific embodiment
The invention will be further described with reference to embodiments.
1. the production of iron-phosphorus non-crystalline alloy catalytic reactor
(1) preparation process of draw and insert-type catalytic reactor
1) production of iron phosphorus non-crystalline alloy coating
(a) metal substrate uses brass sheet, the degreasing of brass surface and oxidation film removal；
(b) electroplate liquid forms；1.8 mol/L of ferrous sulfate, 0.4 mol/L of phosphoric acid, 0.6 g/L of neopelex, lemon Lemon acid sodium 0.3g/L, hypophosphorous acid sodium 0.6 mol/L, potassium iodide 1g/L, water surplus；
(c) iron phosphorus non-crystalline alloy coating is prepared using galvanoplastic, anode uses graphite, and electrolyte temperature is 75 DEG C, titrated sulfuric acid Solution makes Ph value 1；
2) removing of amorphous alloy coating
Keep iron phosphorus non-crystalline alloy coating and brass sheet peeling-off using the method for alternating bending；
3) particle is broken
(a) planetary ball mill is utilized, is carried out, will be peeled off by the way of this interval circulation of 5 min of ball milling, 8 min of stalling Amorphous particle carry out ball milling under vacuum conditions, ball milling total time (time comprising ball milling and stalling) is 1 h, and ratio of grinding media to material is 4:1；
(b) it is sieved into the iron phosphorus non-crystalline alloy particle of different thicknesses；
4) molding of draw and insert-type catalysis electrode metallic cover net
Using the stainless steel mesh of 100 mesh, cut, bending, soldering preparation plate cladding metal mesh,
5) injection and encapsulation of Amorphous Alloy Grain
Into plate cladding metal mesh, injection is greater than the iron phosphorus non-crystalline alloy particle of 100 mesh, is then closed using modes such as solderings At cladding metal mesh.
(2) preparation process of tank reactor frame
Tank reactor frame is prepared using sheet brass cutting, punching, bending.
(3) it is assembled into Fe-based amorphous alloy catalysis electrode
Draw and insert-type catalytic reactor is placed in two fixed plates of reactor, Fe-based amorphous alloy catalytic reactor is made.
2. iron-cobalt-phosphorus non-crystalline alloy catalytic reactor
(1) preparation process of draw and insert-type catalytic reactor
1) iron-cobalt-phosphorus non-crystalline alloy coating production
(a) degreasing of 08F surface of thin steel sheet and oxidation film removal；
(b) electroplate liquid forms；Frerrous chloride 3.5mol/L, 0.7 mol/L of boric acid, 2 g/L of sodium citrate, cobaltous sulfate 1.2mol/ L, sodium hypophosphite 0.65mol/L, potassium iodide 1.5g/L, water surplus；
(c) iron-cobalt-phosphorus non-crystalline alloy coating is prepared using Brush Plating, anode uses graphite plate, and electrolyte temperature is 70 DEG C, drop Determining strong acid solution makes Ph value 1, and the relative moving speed of electrode plate is 100 mm/s, and the average current density of electrode plate is 10A/ cm2；
2) removing of amorphous alloy coating
Keep amorphous alloy coating and 08F sheet metal peeling-off using the method for biaxial tension；
3) particle is broken
(a) planetary ball mill is utilized, by the way of this interval circulation of ball milling 3min, stalling 5min, by the amorphous of peeling Carry out ball milling under the conditions of particle nitrogen protection, ball milling total time (time comprising ball milling and stalling) is 0.5 h, ratio of grinding media to material 5: 1；
(b) it is sieved into iron-cobalt-phosphorus non-crystalline alloy particle of different thicknesses；
4) molding of draw and insert-type catalytic reactor metallic cover net
Using the metal mesh of 100 mesh, cut, bending, soldering preparation plate cladding metal mesh,
5) injection and encapsulation of Amorphous Alloy Grain
Into plate cladding metal mesh, injection is greater than iron-cobalt-phosphorus non-crystalline alloy particle of 100 mesh, then using modes such as solderings It closes plate and coats metal mesh.
(2) preparation process of U-shaped reactor frame
Using bronze thin plate, cutting, punching, bending prepare U-shaped reactor frame.
(3) it is assembled into Fe-based amorphous alloy catalysis electrode
Draw and insert-type catalysis electrode plate is placed in two fixed plates of reactor frame, iron-cobalt-phosphorus non-crystalline alloy catalysis reaction is made Device.

Claims (5)

1. a kind of Fe-based amorphous alloy catalytic reactor, which is characterized in that reactor is by reactor frame and draw and insert-type catalysis reaction Device composition, reactor frame section configuration can be coated iron-based non-for structures, draw and insert-type catalytic reactors such as groove profile, U-shapeds by metal mesh The sheet-like particle of peritectic alloy is made, and the specific ingredient of sheet-like particle is Fe35-95 wt %, remaining alloying element is can be with iron one Play the combination of one of element, such as P, Co, Ni, Cr, Mo, W, Re of electro-deposition or multiple element；Reactor frame is by metal Thin plate or polymer preparation molding, are uniformly provided with slot and fixed plate in the both side plate of reactor frame.
2. the production method of Fe-based amorphous alloy catalytic reactor, which comprises the following steps: (1) draw and insert-type is catalyzed The preparation process of reactor；(2) sheet metal or polymer are used, reactor frame is made；(3) draw and insert-type catalytic reactor is set In two fixed plates of reactor frame, Fe-based amorphous alloy catalytic reactor is made.
3. as claimed in claim 2, the preparation process of draw and insert-type catalytic reactor, production stage is 1) Fe-based amorphous alloy plating The preparation of layer；2) keep amorphous alloy coating peeling-off with metal substrate using method mechanically or physically；3) amorphous particle exists Ball milling under the conditions of vacuum or inert protective gas；4) metal mesh is used, cuts, be bent, soldering preparation plate coats metal mesh；5) Fe-based amorphous alloy particle is injected into plate cladding metal mesh, closes plate cladding metal net into pumping using modes such as solderings Insert formula catalytic reactor.
4. as claimed in claim 3, the preparation of Fe-based amorphous alloy coating, which is characterized in that electroplate liquid composition；Main salt is solvable Property ferrous salt 0.5-4.5mol/L, sour 0.2-0.8mol/L, complexing agent 0.5-5g/L, alloying element additive 0.2-4mol/L, Reducing agent 0.5-4g/L, water surplus；Fe-based amorphous alloy coating is prepared using plating or Brush Plating mode, anode using graphite or Stainless steel, electrolyte temperature are 40-90 DEG C, and titration strong acid solution makes Ph value no more than 2.
5. as claimed in claim 3, the ball milling of amorphous particle, which is characterized in that using ball milling (3-10min), stalling (3- 10min) the mode of this interval circulation, or using ball milling when, can add and force cooling ball milling method, and amorphous particle is in vacuum Or under the conditions of inert protective gas, ball milling total time (time comprising ball milling and stalling) is 0.5-3h, ratio of grinding media to material 2-8:1.
CN201710517827.3A 2017-06-29 2017-06-29 A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor Pending CN109208025A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710517827.3A CN109208025A (en) 2017-06-29 2017-06-29 A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710517827.3A CN109208025A (en) 2017-06-29 2017-06-29 A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor

Publications (1)

Publication Number Publication Date
CN109208025A true CN109208025A (en) 2019-01-15

Family

ID=64960770

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710517827.3A Pending CN109208025A (en) 2017-06-29 2017-06-29 A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor

Country Status (1)

Country Link
CN (1) CN109208025A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603038A (en) * 2012-04-11 2012-07-25 苏州科技学院 Electrochemical reactor and method for processing organic pollutant in water
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology
CN107268018A (en) * 2017-06-19 2017-10-20 长沙理工大学 A kind of Fe-based amorphous alloy catalysis electrode and production method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102603038A (en) * 2012-04-11 2012-07-25 苏州科技学院 Electrochemical reactor and method for processing organic pollutant in water
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology
CN107268018A (en) * 2017-06-19 2017-10-20 长沙理工大学 A kind of Fe-based amorphous alloy catalysis electrode and production method

Similar Documents

Publication Publication Date Title
CN107267892B (en) A kind of ni-based amorphous alloy catalysis electrode and production method
CN106756641B (en) A kind of Fe based amorphous alloy powder and its preparation process
Hong et al. High-activity electrodeposited NiW catalysts for hydrogen evolution in alkaline water electrolysis
Beltowska-Lehman et al. Kinetics of Ni–Mo electrodeposition from Ni-rich citrate baths
CN107268018B (en) A kind of Fe-based amorphous alloy catalysis electrode and production method
Halim et al. Electrodeposition and characterization of nanocrystalline Ni-Mo catalysts for hydrogen production
Guo et al. The hydrogen generation from alkaline NaBH4 solution by using electroplated amorphous Co–Ni–P film catalysts
Hassan et al. Electroless Ni–B supported on carbon for direct alcohol fuel cell applications
Chanda et al. Evaluation of Ni-Cr-P coatings electrodeposited on low carbon steel bipolar plates for polymer electrolyte membrane fuel cell
Sun et al. Electrodeposition of Mo-Rich, MoNi alloys from an aqueous electrolyte
CN102703887A (en) Nickel-copper alloy liquid for chemical plating and electroplating and method for preparing nickel-copper alloy noncrystalline-based composite coating
Mollamahale et al. Electrodeposited Ni-W nanoparticles: Enhanced catalytic activity toward hydrogen evolution reaction in acidic media
CN101717951A (en) Cathode-catalyzed electrode producing method in coal electrolyzing, hydrogenizing and liquefying process
Wang et al. Three-dimensional hierarchical nanostructured Cu/Ni–Co coating electrode for hydrogen evolution reaction in alkaline media
Sheu et al. Improve the mechanical properties and wear resistance of Cr-C thin films by adding Al2O3 particles
Altamirano-Garcia et al. Effects of saccharin and anions (SO 4 2−, Cl−) on the electrodeposition of Co–Ni alloys
CN107267891B (en) A kind of cobalt base amorphous alloy catalysis electrode and production method
Wu et al. Galvanostatic electrodeposition of thin-film Ir–Ni electrocatalyst on copper foam for HER performance in alkaline electrolyte
EP3133682A1 (en) Stainless-steel foil for separator of polymer electrolyte fuel cell
CN109208025A (en) A kind of manufacturing method of Fe-based amorphous alloy catalytic reactor
Negem et al. Electroplating of nanocrystalline Ni–Co alloys using cysteine and their electrochemical behaviour in NaOH solution
CN109200951A (en) A kind of catalytic reactor and production method
CN108070886A (en) A kind of Preparation method and use of bimetallic Cu-Bi electro-catalysis denitrification electrode
Yokoshima et al. Micropattern formation for magnetic recording head using electroless CoFeB deposition
CN108977843A (en) A kind of ni-based amorphous alloy catalysis electrode and preparation method thereof

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20190115

WD01 Invention patent application deemed withdrawn after publication