CN102899684A - Preparation method for cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal - Google Patents
Preparation method for cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal Download PDFInfo
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Abstract
The invention relates to a preparation method for a cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal and especially to a preparation method for the cathodic porous catalytic electrode by preparing a nanometer porous titanium dioxide layer on a titanium substrate through anodization and depositing a nickel-tungsten-boron catalyst layer on porous titanium dioxide through electrodeposition, which belongs to the technical field of electrochemical anodization and electrochemical deposition processes. The preparation method comprises the following steps: (1) pretreatment of the metallic titanium substrate; (2) preparation of nanometer porous TiO2 on the surface of the substrate; and (3) deposition of the catalyst layer on porous TiO2. The nanometer porous Ti/TiO2/Ni-W-B combined electrode prepared in the invention has a high specific surface area and high catalytic activity and can effectively improve current density and current efficiency during electrolysis and hydrogenation of coal.
Description
Technical field
The present invention relates to a kind of preparation method of coal electrolyzing hydrogenation liquefaction negative electrode porous supported catalyst electrode, particularly adopt anonizing at titanium matrix preparation nano porous titanium dioxide layer, utilize simultaneously the preparation method of electrodip process negative electrode porous catalytic electrode of nickel deposited-tungsten-boron Catalytic Layer on poriferous titanium dioxide, belong to electrochemical anodic oxidation and electrochemical deposition process technical field.
Background technology
The direct liquefaction of coal is to be mixed with coal slurry with solvent after coal is crushed to certain particle size in advance, 450 ℃ of certain temperatures (〉), (10 ~ 20MPa) times hydrogenation make macromole become micromolecular process to high pressure.Heat of solution, hydrogen transference and three steps of hydrogenation of general experience coal.Wherein, main weak bond fracture, the material that generation can extract of occuring in the heat of solution process.General when temperature reaches 300 ℃ after, the free radical that pyrolysis produces main with catalyst activation hydrogen and/or hydrogen supply dissolvent generation H transfer and stablize.In addition, the heteroatomss such as O, N, S also can be to a certain extent by hydrogenation and removing in the texture of coal.
The electrolytic hydrogenation liquefaction of coal is that coal is carried out the negative electrode hydrogenation in electrolyzer, is converted into the low molecule organic products of solubility, again it is carried out further hydrogenation and obtains utilizable motor spirit and Chemicals.The negative electrode hydrogenation of coal also belongs to the research range of liquidation of coal, as mentioned above, DCL/Direct coal liquefaction generally is under very high temperature and pressure condition, in the presence of catalyzer and hydrogen supply dissolvent, coal hydrogenation is converted into the course of processing of liquid fuel and Chemicals, and the reduction of the electrochemical hydrogenation of coal is to utilize electric field potential energy to replace the condition of high temperature and high pressure.Have the operational condition gentleness, equipment requirements is simple, the advantage that Financial cost is low.
Realize the electrochemical hydrogenation of coal, at first will solve the optimal selection problem of reactive system, this comprises the selection of design, electrode materials and barrier film of selection, the electrolyzer of solvent in the electrolytic solution.Wherein, work cathode material with and condition of surface coal electrolyzing hydrogenation liquefaction tool is had a great impact.For the selection of negative electrode very early existing document report for work.Fuchs etc. make negative electrode with lead, in the LiOH of the 1M aqueous solution coal are carried out the electrolytic hydrogenation reduction, and finding finally can be with 95% coal dissolving, and the negative electrode working electrode that he selects is stereotype.Given and Peover make negative electrode with the Hg pond, 0.1M the dimethyl methyl phthalein amine aqueous solution of tetraethyl-iodate amine make ionogen, coal is carried out the catholyte hydrogenating reduction, the result shows after the coal electrolysis, per 100 carbon atoms can add 8 hydrogen atoms, when adding a small amount of phenol when doing for the proton body ,-1.0V and-diffusion current at 2.07V place all has increase, this shows that the product after the electrolysis is combined with proton rapidly, and per 100 contained numbers of hydrogen atoms of carbon atom rise to 14.Markby has done more deep widely research for the electrochemical reduction of coal, and he adopts carbon to make anode, makes negative electrode with carbon-point, stone mill, platinum respectively, take LiCl as supporting electrolyte, has done the electrochemical reduction of coal in ethylenediamine solution.Current efficiency is 46% during beginning, and electrolysis dropped to 10% after 15 hours.The human Al such as Sternberg make negative electrode, carry out the electrolytic reduction coal slurry in saturated LiCl solution.The result shows, has added 53 H atoms on per 100 C atoms.Because reaction is what to carry out under very strict condition, so most of Ppolynuclear aromatic carbohydrate all has been reduced with carbonyl group.
Efficiently, the technology of most critical is exactly efficient, stable electrode catalyst in the electrochemistry novel method of the coal electrolyzing hydrogenation of cleaning.The employed working electrode of negative electrode hydrogenation liquefaction for coal mostly was the monometallic plate electrode in the past, and kind electrode has lower electrode specific surface area, has reduced the contact probability of coal and electrode.The key that studies show that high-ratio surface, highly active cathod catalyst is the nanometer size effect of catalyzer, on catalyzer electrocatalytic hydrogenation performance and have significantly impact.Therefore searching and preparation high-ratio surface, highly active electrode materials are the key factors that improves coal electrochemical conversion utilization ratio.
Summary of the invention
Defective for the prior art existence, the object of the present invention is to provide a kind of preparation method of coal electrolyzing hydrogenation liquefaction negative electrode porous supported catalyst electrode, electrooxidation prepares one deck porous nano titanium dioxide on metallic titanium matrix first, then prepares Catalytic Layer with electrodip process on poriferous titanium dioxide.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of coal electrolyzing hydrogenation liquefaction negative electrode porous supported catalyst electrode, concrete steps are as follows:
The pre-treatment of a, metallic titanium matrix: at first metallic titanium matrix is carried out sanding and polishing, then rinse well with deionized water, being put in the acetone ultrasonic wave oil removing cleaned 5 minutes, after with deionized water metallic titanium matrix being rinsed well, again metallic titanium matrix is placed on volume ratio and is in 5% the HF aqueous solution and soaked 30 seconds, put into subsequently volume ratio and be 30% the HCl aqueous solution and cleaned 1 minute, clean up again dry for standby with deionized water;
B, matrix surface nanoporous TiO
2Preparation: adopt two electrode systems, the pretreated matrix of step a put into the aqueous sulfuric acid of 1 mol/L for preparing, as working electrode; Take graphite flake as to electrode, use high pressure DC direct supply to be electrolysis power; At room temperature, the regulating power source voltage knob rises to the voltage of 120V with the speed of 500mV/s, and oxidation 20 minutes obtains nanoporous TiO
2, as porous layer in the middle of the catalysis electrode;
C, nanoporous TiO
2On carry out Catalytic Layer deposition: in electrolyzer, take the Ni sheet for to electrode, the Catalytic Layer electroplate liquid that adding prepares in advance; Regulator solution pH value is 7.0-7.5, under 60 ℃, with 2A/dm
2Electric current deposition 8 minutes, prepare the compound cathode catalysis electrode of nanoporous.
Above-mentioned nanoporous TiO
2Carrying out Catalytic Layer on the film, to deposit added solution be single nickel salt, sodium wolframate, dimethyamine borane and citric acid ammonia; Described 100ml plating bath contains 3g nickel sulfate hexahydrate, 6.5g tungstate dihydrate acid sodium, 1.5g dimethyamine borane, 10g citric acid ammonia.
Compared with prior art, the present invention has following outstanding characteristics:
Owing between matrix titanium and the Catalytic Layer one deck nanoporous TiO is arranged
2Film is as middle supporting layer, so increased to a great extent the specific surface area of electrode, can hold more Catalytic Layer nano particle, effectively increased the probability of collision of electrode surface Catalytic Layer material and coal particle, therefore this structure has the unrivaled advantage of ordinary flat electrode, thereby has improved to a great extent the catalytic activity of electrode.
Description of drawings
Fig. 1 is that the present invention obtains nanoporous Ti/ TiO
2The SEM Electronic Speculum figure on surface.
Fig. 2 is that the present invention obtains nanoporous Ti/ TiO
2The X-ray diffractogram on surface.
Fig. 3 is that the present invention obtains nanoporous Ti/ TiO
2The SEM Electronic Speculum figure on/Ni-W-B surface.
Fig. 4 is that the present invention obtains nanoporous Ti/ TiO
2The X-ray diffractogram on/Ni-W-B surface.
Fig. 5 is negative electrode porous catalytic electrode of the present invention and the I-V curve of other Different electrodes in coal electrolytic hydrogenation process.
Embodiment
After now embodiments of the present invention specifically being described in.
Embodiment 1
Present embodiment is Ti/ TiO
2The preparation of negative electrode porous catalytic electrode.Its preparation process is as follows:
(1) pre-treatment of metallic titanium matrix: at first metallic titanium matrix is carried out sanding and polishing, then rinse well with deionized water, being put in the acetone ultrasonic wave oil removing cleaned 5 minutes, after with deionized water matrix being rinsed well, again matrix is placed in 5% the HF aqueous solution and soaked 30 seconds, put into subsequently 30% the HCl aqueous solution and processed 1 minute, clean up again dry for standby with deionized water.
(2) titanium matrix surface nanoporous TiO
2Preparation: adopt two electrode systems, above-mentioned pretreated titanium matrix put into the aqueous sulfuric acid of 1 mol/L for preparing, and as working electrode; Take graphite flake as to electrode, use high pressure DC direct supply to be electrolysis power.At room temperature, the regulating power source voltage knob rises to the voltage of 120V, oxidation 20 minutes with the speed of 500mV/s.
The resulting nanoporous Ti/TiO of present embodiment
2The SEM Electronic Speculum figure on surface sees Fig. 1, and X-ray diffractogram is seen Fig. 2.
Embodiment 2
Present embodiment is Ti/TiO
2The preparation of/Ni-W-B negative electrode porous catalytic electrode.
First two steps and the first two steps in above-described embodiment of present embodiment are identical.The different bases in first two steps have added (3) steps-porous TiO
2On carry out Catalytic Layer deposition: in electrolyzer, for to electrode, the 100ml plating bath contains 3g nickel sulfate hexahydrate, the sour sodium of 6.5g tungstate dihydrate, 1.5g dimethyamine borane, 10g citric acid ammonia take the Ni sheet, and adjusting PH is 7.0-7.5, and temperature is 60 ℃, with 2A/dm
2Electric current deposition 8 minutes, regulate the thickness of coating by the control depositing time, prepare nanoporous Ti/TiO
2The cathode catalysis electrode that/Ni-W-B is compound.Regulate the thickness of coating by the control depositing time.
The resulting nanoporous Ti/TiO of present embodiment
2The SEM Electronic Speculum figure on/Ni-W-B catalysis electrode surface sees Fig. 3, and X-ray diffractogram is seen Fig. 4.
Embodiment 3
The cathode catalysis electrode that the embodiment of the invention makes and the contrast experiment of other Different electrodes; The I-V curve of test Different electrodes in the electrolyzing coal slurry process.
Present embodiment is the preparation of Ti/Ni-W-B cathode catalysis electrode.
(1) step of present embodiment is identical with (1) step in above-described embodiment.Different is that the Ti sheet of directly handling well with (1) step in (2) step replaces (3) the nanoporous Ti/ TiO that goes on foot
2, galvanic deposit is 8 minutes in the same terms and plating bath.Regulate the thickness of coating by the control depositing time.
The concrete experiment condition of prepared electrode catalyst active testing is: coal-water fluid concentration is 20g/L, and electrolytic solution is DMF and ethanol (volume ratio is 2:3), and supporting electrolyte is 0.5mol/L
-1Tetrabutyl amonium bromide, the proton hydrogen supply agent is 2.5 mol/L
-1Deionized water, temperature is 50 ℃; Take platinum electrode as to electrode, test electrode is the work negative electrode, and saturated calomel electrode is reference electrode, adopts three-electrode system; Use the CHI660B Electrochemical Comprehensive Tester to test.Test result is seen Fig. 5, and Fig. 5 is cathode catalysis electrode of the present invention and the I-V curve comparison diagram of other Different electrodes in the electrolyzing coal slurry process.
Fig. 5: the I-V curve of a:Ti plate electrode
B: nanoporous Ti/TiO
2The I-V curve of electrode
The I-V curve of c:Ti/Ni-W-B electrode
D: nanoporous Ti/TiO
2The I-V curve of/Ni-W-B electrode
As can be seen from Figure 5, the prepared nanoporous Ti/ of the present invention TiO
2/ Ni-W-B catalysis electrode has higher current density, can effectively improve the efficient of electrolysis coal.
Claims (2)
1. the preparation method of a coal electrolyzing hydrogenation liquefaction negative electrode porous supported catalyst electrode is characterized in that concrete steps are as follows:
The pre-treatment of metallic titanium matrix: at first metallic titanium matrix is carried out sanding and polishing, then rinse well with deionized water, being put in the acetone ultrasonic wave oil removing cleaned 5 minutes, after with deionized water metallic titanium matrix being rinsed well, again metallic titanium matrix is placed on volume ratio and is in 5% the HF aqueous solution and soaked 30 seconds, put into subsequently volume ratio and be 30% the HCl aqueous solution and cleaned 1 minute, clean up again dry for standby with deionized water;
B, matrix surface nanoporous TiO
2Preparation: adopt two electrode systems, the pretreated matrix of step a put into the aqueous sulfuric acid of 1 mol/L for preparing, as working electrode; Take graphite flake as to electrode, use high pressure DC direct supply to be electrolysis power; At room temperature, the regulating power source voltage knob rises to the voltage of 120V with the speed of 500mV/s, and oxidation 20 minutes obtains nanoporous TiO
2, as porous layer in the middle of the catalysis electrode;
C, nanoporous TiO
2On carry out Catalytic Layer deposition: in electrolyzer, take the Ni sheet for to electrode, the Catalytic Layer electroplate liquid that adding prepares in advance; Regulator solution pH value is 7.0-7.5, under 60 ℃, with 2A/dm
2Electric current deposition 8 minutes, prepare the compound cathode catalysis electrode of nanoporous.
2. the preparation method of a kind of coal electrolyzing hydrogenation liquefaction negative electrode porous supported catalyst electrode as claimed in claim 1 is characterized in that described Catalytic Layer electroplate liquid is single nickel salt, sodium wolframate, dimethyamine borane and citric acid ammonia; Described 100ml plating bath contains 3g nickel sulfate hexahydrate, 6.5g tungstate dihydrate acid sodium, 1.5g dimethyamine borane, 10g citric acid ammonia.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104562076A (en) * | 2015-01-23 | 2015-04-29 | 上海大学 | Method for preparing cathode catalysis electrode in coal electrolysis hydrogenation liquefaction |
| CN111378986A (en) * | 2020-04-02 | 2020-07-07 | 上海大学 | Preparation method of porous lead composite nickel-iron alloy catalytic electrode and application of porous lead composite nickel-iron alloy catalytic electrode in coal electrolysis liquefaction |
| CN112717948A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Boron modified hydrofining catalyst and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562076A (en) * | 2015-01-23 | 2015-04-29 | 上海大学 | Method for preparing cathode catalysis electrode in coal electrolysis hydrogenation liquefaction |
| CN104562076B (en) * | 2015-01-23 | 2018-05-01 | 上海大学 | Preparation method for the cathode catalysis electrode in coal electrolyzing hydrogenation liquefaction |
| CN112717948A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Boron modified hydrofining catalyst and preparation method and application thereof |
| CN112717948B (en) * | 2019-10-28 | 2023-05-05 | 中国石油化工股份有限公司 | Boron modified hydrofining catalyst and preparation method and application thereof |
| CN111378986A (en) * | 2020-04-02 | 2020-07-07 | 上海大学 | Preparation method of porous lead composite nickel-iron alloy catalytic electrode and application of porous lead composite nickel-iron alloy catalytic electrode in coal electrolysis liquefaction |
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