CN109200951A - A kind of catalytic reactor and production method - Google Patents
A kind of catalytic reactor and production method Download PDFInfo
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- CN109200951A CN109200951A CN201710517828.8A CN201710517828A CN109200951A CN 109200951 A CN109200951 A CN 109200951A CN 201710517828 A CN201710517828 A CN 201710517828A CN 109200951 A CN109200951 A CN 109200951A
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- catalytic reactor
- draw
- insert
- amorphous alloy
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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- 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
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- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of catalytic reactor is made of groove profile frame and draw and insert-type catalytic reactor, draw and insert-type catalytic reactor is made of the sheet-like particle of metal mesh cladding ni-based amorphous alloy, the specific ingredient of ni-based amorphous alloy sheet-like particle is Ni30-95 wt %, remaining alloying element be can together with Ni one of element, such as P, Co, Fe, Cr, Mo, W, Re of electro-deposition or multiple element combination；Groove profile frame two sides plate face is uniformly provided with slot and fixed plate.The production method of reactor the following steps are included: (1) draw and insert-type catalytic reactor preparation process；(2) sheet metal or plastics are used, groove profile arc-spark stand is processed into；(3) draw and insert-type catalytic reactor is placed in two fixed plates, catalytic reactor is made.
Description
Technical field
The present invention relates to the catalysis electrode of electrochemical field, it is related specifically to a kind of catalytic reactor and production method.
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 catalytic reactor and production method.Technical solution of the invention
It is to provide a kind of catalytic reactor, which is characterized in that reactor is made of groove profile frame and draw and insert-type catalytic reactor, and draw and insert-type is urged
Change reactor to be made of the sheet-like particle of metal mesh cladding ni-based amorphous alloy, the specific ingredient of ni-based amorphous alloy sheet-like particle
For Ni30-95 wt %, remaining alloying element be can together with Ni electro-deposition element, such as in P, Co, Fe, Cr, Mo, W, Re
One or more elements combination.The two sides plate face of groove profile frame is uniformly provided with slot and fixed plate.
The technical solution of the invention is as follows provides a kind of preparation method of catalytic reactor again, comprising the following steps:
(1) preparation process of draw and insert-type catalytic reactor
1) production of nickel-base 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 be soluble nickel 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, water surplus；
In the upper alloying element additive, iron is with ferrous sulfate or frerrous chloride (need to be furnished with reducing agent), cobalt with cobaltous sulfate, chromium
Added in the form of Re soluble salt by sodium tungstate, phosphorus by phosphorous acid or soluble hypophosphites, Re by chromic anhydride, molybdenum by sodium molybdate, tungsten
Add；
Above-mentioned acid includes the polynary middle strong acid such as boric acid, phosphoric acid；
Above-mentioned complexing agent includes the carboxyls Barbiturates complexing agent such as tartaric acid, citrate；
(c) ni-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) using ball mill, planetary ball mill etc., the amorphous particle of peeling is subjected to ball under the conditions of vacuum or protective gas
Mill, by the way of ball milling (3-10min), this interval stalling (3-10min) circulation, or in ball milling can to add pressure simultaneously cold
But mode carries out ball milling, and 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 ni-based amorphous alloy particle of different thicknesses；
4) molding of draw and insert-type catalysis electrode metallic cover net
Using metal mesh, cut, bending, soldering preparation cladding metal mesh,
5) injection and encapsulation of Amorphous Alloy Grain
Ni-based amorphous alloy particle is injected into cladding metal mesh, then closes cladding metal mesh using modes such as solderings.
(2) preparation process of groove profile frame
Using sheet metal or plastics, it is processed into groove profile arc-spark stand.
(3) it is assembled into ni-based amorphous alloy catalysis electrode
Draw and insert-type catalytic reactor is placed in two fixed plates, ni-based amorphous alloy catalytic reactor is made.
Compared with prior art, advantages of the present invention:
1. due to, as catalyst, the catalytic performance of reactor can be improved using ni-based amorphous alloy particle；
2. particle basic configuration is lamellar, this raising due to preparing ni-based amorphous alloy particle using plating+removing+broken
The surface area of amorphous alloy catalyst reaction；
3. due to using groove profile frame, and offering slot in both side plate, end is also unclosed, improves solution to greatest extent
Or air-flow increases the relative flow of catalytic reactor and reactive material in the flowability of inside reactor, and it is anti-that catalysis can be improved
Answer the catalytic efficiency of device；
4. reactor areas and reactor spacing are easily achieved adjustment, are also convenient for more due to using draw and insert-type structure
It changes and repairs.
Detailed description of the invention
Fig. 1 is present device schematic diagram.Wherein, groove profile frame (1), can gold mining metal thin plate be made；Can draw and insert-type catalysis it is anti-
Device (2) are answered, are made of metal mesh cladding ni-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 nickel-phosphor amorphous alloy catalytic reactor
(1) preparation process of draw and insert-type catalytic reactor
1) production of nickel phosphorus non-crystal alloy layer
(a) metal substrate uses brass sheet, the degreasing of brass surface and oxidation film removal；
(b) electroplate liquid forms；1.6 mol/L of nickel sulfate, 0.4 mol/L of phosphoric acid, 1.2 g/L of tartaric acid, sodium citrate 0.4g/L,
0.6 mol/L of hypophosphorous acid sodium, water surplus；
(c) nickel phosphorus non-crystal alloy layer is prepared using galvanoplastic, anode uses graphite, and electrolyte temperature is 65 DEG C, titrated sulfuric acid
Solution makes Ph value 1, and electrode average current density is 1.2A/cm2；
2) removing of amorphous alloy coating
Keep nickel-phosphorus alloy coating peeling-off with brass sheet using the method for alternating bending；
3) particle is broken
(a) it is carried out by the way of this interval circulation of 5 min of ball milling, 8 min of stalling, by the amorphous particle of peeling in vacuum item
Ball milling is carried out under part, ball milling total time (time comprising ball milling and stalling) is 1 h, ratio of grinding media to material 4:1；
(b) it is sieved into the nickel phosphorus non-crystal alloying pellet of different thicknesses；
4) molding of draw and insert-type catalytic reactor 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 nickel phosphorus non-crystal alloying pellet of 100 mesh, is then closed using modes such as solderings
Metal mesh is coated at plate.
(2) preparation process of groove profile frame
Using sheet brass cutting, punching, bending preparation vessel type frame.
(3) it is assembled into ni-based amorphous alloy catalytic reactor
Draw and insert-type catalytic reactor is placed in two fixed plates, catalytic reactor is made.
2. Ni-Fe-phosphorus non-crystalline alloy catalytic reactor
(1) preparation process of draw and insert-type catalytic reactor
1) Ni-Fe-phosphorus non-crystalline alloy coating production
(a) degreasing of 08F surface of thin steel sheet and oxidation film removal；
(b) electroplate liquid forms；Nickel chloride 3.5mol/L, 0.7 mol/L of boric acid, 2 g/L of sodium citrate, ferrous sulfate 1.2mol/
L, sodium hypophosphite 0.65mol/L, potassium iodide 1.5g/L, water surplus；
(c) Ni-Fe-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 0.5, and the relative moving speed of electrode plate is 100 mm/s, and the average current density of electrode plate is 15
A/cm2；
2) removing of amorphous alloy coating
Keep amorphous alloy coating peeling-off with steel plate using the method for biaxial tension；
3) particle is broken
(a) planetary ball mill is used, by the way of this interval circulation of ball milling 3min), stalling 5min, by the amorphous of peeling
Ball milling is carried out under the conditions of particle nitrogen protection, ball milling can be 0.5 h, ball material ball milling total time (time comprising ball milling and stalling)
Than for 5:1；
(b) it is sieved into Ni-Fe-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 Ni-Fe-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 groove profile frame
Using bronze thin plate, cutting, punching, bending preparation vessel type frame.
(3) it is assembled into ni-based amorphous alloy catalytic reactor
Draw and insert-type catalytic reactor is placed in two fixed plates, Ni-Fe-phosphorus non-crystalline alloy catalytic reactor is made.
Claims (5)
1. a kind of catalytic reactor, which is characterized in that reactor is made of groove profile frame and draw and insert-type catalytic reactor, and draw and insert-type is urged
Change reactor to be made of the sheet-like particle of metal mesh cladding ni-based amorphous alloy, the specific ingredient of ni-based amorphous alloy sheet-like particle
For Ni30-95 wt %, remaining alloying element be can together with Ni electro-deposition element, such as in P, Co, Fe, Cr, Mo, W, Re
One or more elements combination；Groove profile frame two sides plate face is uniformly provided with slot and fixed plate.
2. the production method of catalytic reactor, which comprises the following steps: (1) preparation of draw and insert-type catalytic reactor
Technique；(2) sheet metal or plastics are used, groove profile arc-spark stand is processed into；(3) draw and insert-type catalytic reactor is placed in two fixed plates
In, catalytic reactor is made.
3. described in claim 2, the preparation process of draw and insert-type catalytic reactor, which is characterized in that production stage is 1) Ni-based conjunction
The production of golden amorphous deposit；2) using mechanically or physically keeps amorphous alloy coating peeling-off with metal substrate；3) amorphous particle
Ball milling is carried out under the conditions of vacuum or protective gas；4) metal mesh is used, is cut, bending, soldering preparation cladding metal mesh；5) past
It coats and injects ni-based amorphous alloy particle in metal mesh, then close cladding metal mesh using modes such as solderings.
4. described in claim 3, the preparation process of nickel-base alloy amorphous deposit, which is characterized in that (b) electroplate liquid composition；Main salt
For soluble nickel 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, water surplus；Ni-based amorphous alloy coating is prepared using plating or Brush Plating, anode uses graphite or stainless steel, electrolysis
Liquid temperature is 40-90 DEG C, and titration strong acid solution makes Ph value no more than 2；
In the upper alloying element additive, iron is with ferrous sulfate or frerrous chloride (need to be furnished with reducing agent), cobalt with cobaltous sulfate, chromium
Added in the form of Re soluble salt by sodium tungstate, phosphorus by phosphorous acid or soluble hypophosphites, Re by chromic anhydride, molybdenum by sodium molybdate, tungsten
Add.
5. described 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 can be added simultaneously in ball milling and cooling mode is forced to carry out ball milling, ball milling total time (includes ball
The time of mill and stalling) it is 0.5-3h, ball material mass ratio is 2-8:1.
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| CN201710517828.8A CN109200951A (en) | 2017-06-29 | 2017-06-29 | A kind of catalytic reactor and production method |
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| CN201710517828.8A CN109200951A (en) | 2017-06-29 | 2017-06-29 | A kind of catalytic reactor and production method |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104496A (en) * | 1985-07-03 | 1986-12-31 | 标准石油公司 | The manufacture method of amorphous multi-metal alloy coatings |
| CN1152475A (en) * | 1995-12-20 | 1997-06-25 | 中国石油化工总公司石油化工科学研究院 | High-ferromagnetic non-crystalline alloy catalyst |
| CN1265605A (en) * | 1997-08-08 | 2000-09-06 | Abb拉默斯环球有限公司 | Reactor including mesh structure for supporting catalytic particles |
| WO2007120205A2 (en) * | 2005-11-14 | 2007-10-25 | The Regents Of The University Of California | Compositions of corrosion-resistant fe-based amorphous metals suitable for producing thermal spray coatings |
| CN101532153A (en) * | 2009-03-13 | 2009-09-16 | 甘军 | Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process |
| CN105226299A (en) * | 2014-06-27 | 2016-01-06 | 福特全球技术公司 | Oxygen reduction reaction catalyst |
| CN106893954A (en) * | 2017-03-21 | 2017-06-27 | 长沙理工大学 | Co-based amorphous alloy powder and preparation process thereof |
-
2017
- 2017-06-29 CN CN201710517828.8A patent/CN109200951A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104496A (en) * | 1985-07-03 | 1986-12-31 | 标准石油公司 | The manufacture method of amorphous multi-metal alloy coatings |
| CN1152475A (en) * | 1995-12-20 | 1997-06-25 | 中国石油化工总公司石油化工科学研究院 | High-ferromagnetic non-crystalline alloy catalyst |
| CN1265605A (en) * | 1997-08-08 | 2000-09-06 | Abb拉默斯环球有限公司 | Reactor including mesh structure for supporting catalytic particles |
| WO2007120205A2 (en) * | 2005-11-14 | 2007-10-25 | The Regents Of The University Of California | Compositions of corrosion-resistant fe-based amorphous metals suitable for producing thermal spray coatings |
| CN101532153A (en) * | 2009-03-13 | 2009-09-16 | 甘军 | Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process |
| CN105226299A (en) * | 2014-06-27 | 2016-01-06 | 福特全球技术公司 | Oxygen reduction reaction catalyst |
| CN106893954A (en) * | 2017-03-21 | 2017-06-27 | 长沙理工大学 | Co-based amorphous alloy powder and preparation process thereof |
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Application publication date: 20190115 |