CN103480420A - Method for preparing cathode supported catalyst in coal electrochemical hydrogenation liquefaction - Google Patents
Method for preparing cathode supported catalyst in coal electrochemical hydrogenation liquefaction Download PDFInfo
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- CN103480420A CN103480420A CN201310424264.5A CN201310424264A CN103480420A CN 103480420 A CN103480420 A CN 103480420A CN 201310424264 A CN201310424264 A CN 201310424264A CN 103480420 A CN103480420 A CN 103480420A
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Abstract
The invention relates to a method for preparing a cathode supported catalyst in coal electrochemical hydrogenation liquefaction, in particular to a method for preparing an amorphous NiB catalyst supported on SiO2 through a chemical reduction method, and belongs to the technical field of catalysts and preparation and application of the catalysts. The method for preparing the cathode supported catalyst in coal electrochemical hydrogenation liquefaction comprises the steps: (1) preprocessing the carrier SiO2, (2) preparing a solution, (3) generating the amorphous catalyst, (4) washing the amorphous catalyst, and (5) storing the amorphous catalyst. The prepared amorphous PVP-NiB/SiO2 catalyst has a larger specific area and higher catalytic activity, and can effectively improve current density and current efficiency of coal electrochemical hydrogenation.
Description
Technical field
The present invention relates to the preparation method of the cathode load type catalyst in a kind of coal electrolyzing hydrogenation liquefaction, particularly adopt chemical reduction method at SiO
2the preparation method of upper supported amorphous NiB catalyst, the technical field of metal catalyst and preparation thereof and application.Such catalyst can improve current density and the current efficiency of coal electrolyzing hydrogenation effectively.
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, at uniform temperature (~ 450 ℃), the lower hydrogenation of high pressure (10 ~ 20 MPa), makes large molecule become micromolecular process.Heat of solution, hydrogen migration and three steps of hydrogenation of general experience coal.Wherein, main weak bond fracture, the material that generation can extract of occurring in the heat of solution process.General after temperature reaches 300 ℃, H occurs for the hydrogen that the free radical that pyrolysis produces is main and catalyst activates and/or hydrogen supply dissolvent shifts and stablizes.In addition, in texture of coal, the hetero atoms such as O, N, S also can be to a certain extent by hydrogenation and removing.
The liquefaction of the electrolytic hydrogenation of coal is coal to be carried out in electrolytic cell to the negative electrode hydrogenation, is converted into the low molecule organic products of solubility, then it is carried out to further hydrogenation obtains utilizable engine fuel and chemical products.The negative electrode hydrogenation of coal also belongs to the research range of lique faction of coal, as mentioned above, DCL/Direct coal liquefaction is generally under very high temperature and pressure condition, coal hydrogenation is converted into to the process of liquid fuel and chemical products under the existence of catalyst and hydrogen supply dissolvent, 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 operating condition gentleness, equipment requirement is simple, the advantage that financial cost is low.
Realize the electrochemical hydrogenation of coal, at first will solve the optimal selection problem of reaction system, this comprises the selection of design, electrode material and barrier film of selection, the electrolytic cell of solvent in electrolyte, and the utilization of catalyst.Wherein, cathod catalyst plays vital effect in the Coal Liquefaction reaction.The effect of catalyst when coal liquefaction is mainly to reduce activation energy, accelerated reaction; The promotion solvent fully contacts with coal particle, thereby makes solvent become the donor of reactive hydrogen.Good catalyst can reduce the coal liquefaction temperature, reduces side reaction and reduces energy consumption, increases the yield of product liquid.In addition, adding of catalyst also can improve the transfer rate that activates hydrogen, suppresses the free radical polycondensation, removes the hetero atoms such as N in coal liquid, O, S simultaneously, improves product quality.
Coal liquefaction is heterogeneous catalytic reaction, and the contact condition between catalyst and reactant is very important.From the coal liquefaction course, it is a vital step for obtaining high conversion that activation hydrogen transmits coal supply free radical fragment.At the liquefaction reaction initial stage, the free radical fragment of coal often exists with the macromolecular form of melting, owing to being subject to spatial limitation, and the easy polycondensation of these free radical fragments.Therefore, the exposure level between increase catalyst and solid coal particle is conducive to the carrying out of hydrogen transmittance process.In Coal liquefaction, the effect of catalyst has produced active hydrogen atom just, by solvent, be the indirect branch that medium has been realized hydrogen again, make various liquefaction reactions smooth, its effect mainly contains following 3 points: (1) activated reactant, accelerate hydrogenation reaction speed, improve conversion ratio and the oily yield of coal liquefaction; (2) promote the repeated hydrogenation of solvent and the hydrogen transmission between hydrogen source and coal; (3) selective.In order to improve oily yield and oil quality, reduce residue and gaseous hydrocarbon productive rate, require catalyst to there is the selective catalysis effect, wish that catalyst accelerates thermal cracking, hydrogenation, removes hetero atom, isomerization reaction, suppress dehydrogenation and condensation reaction and carry out.
At present, the catalyst used in coal liquefaction has three major types usually.The first kind is cobalt (Co), molybdenum (Mo), nickel (Ni) catalyst, and catalytic activity is higher; Equations of The Second Kind is metal halide catalyst, as ZnCl
2, SnCl
2deng, belonging to acidic catalyst, cracking ability is strong; The 3rd class is Fe-series catalyst, comprises the natural crystal of iron content, the industrial residu of iron content and the compound (as oxide, sulfide and the hydroxide of iron) of various pure state iron.According to lot of documents report Ni series catalysts, hydrogenation is had to significant effect, become the focus that domestic and international researcher pays close attention to, but apply it to coal liquefaction, the especially research of coal electrolytic hydrogenation liquefaction aspect but seldom.Therefore, we develop a kind of efficient coal electrolytic hydrogenation liquefaction cathode load type catalyst tool and are of great significance.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of cathode load type catalyst n iB, and apply it in the coal electrolyzing hydrogenation liquefaction.
Characteristics of the present invention are that first the business column layer chromatography silicone rubber being carried out to pretreatment obtains carrier S iO
2, and then on carrier, utilize the amorphous catalyst of chemical preparation, PVP in course of reaction (PVP) to play and disperse and stable effect.Method for preparing catalyst of the present invention is simple, and easy operating can improve current density and the current efficiency of coal electrolyzing hydrogenation effectively.
The preparation method of cathode load type catalyst n iB in a kind of coal electrolyzing hydrogenation liquefaction of the present invention is characterized in that following technical process and step are arranged:
A, carrier S iO
2pretreatment: at first 300～400 order business column layer chromatography silicone rubbers are carried out to roasting, the detailed process of roasting is warming up to 400 ℃ with 5 ℃ per minute, then roasting obtains carrier S iO after 5 hours in Muffle furnace
2;
The configuration of b, nickel salt solution: the Ni that at first prepares 0.05 M～0.5 M
2+the aqueous solution, then by appropriate Mr=58000 PVPs (PVP) powder and 0.1 g～good SiO of 0.4 g pretreatment
2add in nickel salt aqueous solution, stir 3～5 hours; The mass ratio of two materials is PVP: Ni
2+=(8～10): 1;
The generation of c, amorphous catalyst NiB: utilize constant flow pump to drip speed with 2～5 r/min the solution in step 2 is added to isopyknic 0.5 M～5 M B
3+in the aqueous solution, vigorous stirring; Reaction is carried out and releasing hydrogen gas immediately, generates black precipitate; Reaction at room temperature, is carried out in three-necked bottle; Both mass ratioes are Ni
2+: B
3+=1: (1～1.5);
The washing of d, amorphous catalyst NiB: after no hydrogen is emitted, utilize centrifuge to isolate sediment with 2000～8000 r/min, and with after deionized water washing three times, then use the ethanol washed twice;
The preservation of e, amorphous catalyst NiB: the sediment washed is kept in absolute ethyl alcohol, stand-by.
Ni in above-mentioned steps b
2+can be at least one in nickel acetate, nickelous sulfate, nickel chloride and nickel nitrate.B in step c
3+can be NaBH
4or KBH
4in at least one.
The characteristics of the inventive method are: take PVP as dispersant and stabilizing agent, with SiO
2for carrier, suppressed to a great extent the reunion of catalyst, reduced particle diameter, increased specific area, improved active component.This preparation method is simple, easy operating, and reproducible.
The accompanying drawing explanation
Fig. 1 is the amorphous state NiB that the present invention obtains, PVP-NiB, PVP-NiB/SiO
2the XRD collection of illustrative plates of catalyst.
Fig. 2 is the amorphous state NiB that the present invention obtains, PVP-NiB, PVP-NiB/SiO
2the FTIR collection of illustrative plates of catalyst.
Fig. 3 is the amorphous state NiB that the present invention obtains, PVP-NiB, PVP-NiB/SiO
2the I-V curve map of catalyst in coal electrolytic hydrogenation process.
The specific embodiment
After now embodiments of the present invention specifically being described in.
The present embodiment is PVP-NiB/SiO
2the preparation of cathod catalyst.
1, carrier S iO
2pretreatment: at first 300～400 order business column layer chromatography silicone rubbers are carried out to roasting, the detailed process of roasting is warming up to 400 ℃ with 5 ℃ per minute, then roasting obtains carrier S iO after 5 hours in Muffle furnace
2.
2, the configuration of nickel salt solution: at first prepare the nickel acetate aqueous solution of 0.1 M, then by appropriate Mr=58000 PVPs (PVP) powder and the good SiO of 0.3 g pretreatment
2add in nickel salt aqueous solution, stir 3 hours.Mass ratio is nickel acetate: PVP=1: 8.88.
3, the generation of amorphous catalyst NiB: utilize constant flow pump to drip speed with 3 r/min the solution in step 2 is added to isopyknic NaBH
4in the aqueous solution, vigorous stirring.Reaction is carried out and releasing hydrogen gas immediately, generates black precipitate.Reaction at room temperature, is carried out in three-necked bottle.Mass ratio is nickel acetate: NaBH
4=1: 1.5.
4, the washing of amorphous catalyst NiB: after no hydrogen is emitted, utilize centrifuge to isolate sediment with 8000 r/min, and with after deionized water washing three times, then use the ethanol washed twice.
5, the preservation of amorphous catalyst NiB: the sediment washed is kept in absolute ethyl alcohol, stand-by.
The resulting amorphous state PVP-NiB/SiO of the present embodiment
2fig. 1 is shown in by the XRD collection of illustrative plates of catalyst, and chemical composition and specific area are shown in Fig. 2 in Table 1, FTIR (Fu Shi changes infrared spectrum).
comparative Examples 1
?the preparation that this Comparative Examples is the NiB cathod catalyst.Its preparation process is as follows:
1, the configuration of solution: configure the 0.1 M nickel acetate aqueous solution.
2, the generation of amorphous state NiB catalyst: utilize constant flow pump, with the speed of dripping of 3 r/min, the solution in step 1 is added to isopyknic 1 M NaBH
4in the aqueous solution, vigorous stirring.Reaction is carried out and releasing hydrogen gas immediately, generates black precipitate.Reaction at room temperature, is carried out in three-necked bottle.Mass ratio is nickel acetate: NaBH
4=1: 1.5.
3, the washing of amorphous state NiB catalyst: after no hydrogen is emitted, utilize centrifuge to isolate sediment with 8000 r/min, and with after deionized water washing three times, then use the ethanol washed twice.
4, the preservation of amorphous state NiB catalyst: the sediment NiB washed is kept in absolute ethyl alcohol.
Fig. 1 is shown in by the XRD collection of illustrative plates of the resulting amorphous state NiB catalyst of the present embodiment, and chemical composition and specific area are shown in Fig. 2 in Table 1, FTIR (Fu Shi changes infrared spectrum).
comparative Examples 2
The preparation that this Comparative Examples is the PVP-NiB cathod catalyst.
Rear three steps and rear three steps in Comparative Examples 1 of this Comparative Examples are identical.Different is the 1st step: add PVP (PVP) powder of appropriate Mr=58000 in the 0.1 M nickel acetate aqueous solution, stir 1 hour.Mass ratio is nickel acetate: PVP=1: 8.88.。
Fig. 1 is shown in by the XRD collection of illustrative plates of the resulting amorphous state PVP-NiB catalyst of the present embodiment, and chemical composition and specific area are shown in Fig. 2 in Table 1, FTIR (Fu Shi changes infrared spectrum).
contrast test to each catalyst
Contrast experiment to the various cathod catalysts that make; The I-V curve of test different catalysts in the electrolyzing coal slurry process.
The concrete experiment condition of prepared catalyst catalytic activity test is: coal-water fluid concentration is 0.03 g/ml, the NaOH that electrolyte is 1 M, and temperature is 70 ℃; Take platinum electrode as to electrode, and the iridium dioxide electrode is the work negative electrode, and saturated calomel electrode is reference electrode, adopts three-electrode system; Adopt the CHI660B Electrochemical Comprehensive Tester to be tested.
Test result is shown in Fig. 3, and Fig. 3 is the I-V curve comparison diagram of cathod catalyst of the present invention in the electrolyzing coal slurry process.
Fig. 3: a: the I-V curve of blank assay
the I-V curve of b:NiB catalyst
The I-V curve of c:PVP-NiB catalyst
D:PVP-NiB/SiO
2the I-V curve of catalyst
E: the I-V curve of coal
The I-V curve of f:NiB+coal
The I-V curve of g:PVP-NiB+coal
F:PVP-NiB/SiO
2the I-V curve of+coal
As can be seen from Figure 3, chemical reaction itself does not occur in the prepared catalyst of the present invention, but can effectively improve the current density of coal electrolytic hydrogenation, particularly supported amorphous catalyst PVP-NiB/SiO
2.
Claims (3)
1. the preparation method of the cathode load type catalyst in a coal electrolyzing hydrogenation liquefaction is characterized in that following process engineering and step are arranged:
A, carrier S iO
2pretreatment: at first 300～400 order business column layer chromatography silicone rubbers are carried out to roasting, the detailed process of roasting is warming up to 400 ℃ with 5 ℃ per minute, then roasting obtains carrier S iO after 5 hours in Muffle furnace
2;
The configuration of b, nickel salt solution: at first prepare the nickel salt aqueous solution of 0.05 M～0.5 M, then by appropriate Mr=58000 PVPs (PVP) powder and 0.1 g～good SiO of 0.4 g pretreatment
2add in nickel salt aqueous solution, stir 3～5 hours; The mass ratio of two materials is PVP: Ni
2+=(8～10): 1;
The generation of c, amorphous catalyst NiB: utilize constant flow pump to drip speed with 2～5 r/min the solution in step b is added to isopyknic 0.5 M～5 M B
3+in the aqueous solution, vigorous stirring; Reaction is carried out and releasing hydrogen gas immediately, generates black precipitate; Reaction at room temperature, is carried out in three-necked bottle; Both mass ratioes are Ni
2+: B
3+=1: (1～1.5);
The washing of d, amorphous catalyst NiB: after no hydrogen is emitted, utilize centrifuge to isolate sediment with 2000～8000 r/min, and with after deionized water washing three times, then use the ethanol washed twice;
The preservation of e, amorphous catalyst NiB: the sediment washed is kept in absolute ethyl alcohol, stand-by.
2. according to the preparation method of the cathode load type catalyst in the said a kind of coal electrolyzing hydrogenation liquefaction of claim 1, it is characterized in that described Ni
2+can be at least one in nickel acetate, nickelous sulfate, nickel chloride and nickel nitrate.
3. according to the preparation method of the cathode load type catalyst in the said a kind of coal electrolyzing hydrogenation liquefaction of claim 1, it is characterized in that described B
3+can be NaBH
4or KBH
4in at least one.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399525A (en) * | 2014-11-26 | 2015-03-11 | 上海大学 | Preparation method of hydrogenation catalyst for electrolytic liquidation of coal |
| CN104607192A (en) * | 2015-01-23 | 2015-05-13 | 上海大学 | Coal electrolysis hydro-liquefaction catalyst and preparation method thereof |
| CN110075852A (en) * | 2019-05-15 | 2019-08-02 | 武汉轻工大学 | A kind of preparation method of nanometer amorphous Ni-B catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102614928A (en) * | 2012-03-20 | 2012-08-01 | 昆明理工大学 | Loaded nano amorphous alloy catalyst and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614928A (en) * | 2012-03-20 | 2012-08-01 | 昆明理工大学 | Loaded nano amorphous alloy catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| 姜虹等: "镍硼电极及FeS催化剂对煤电解液化的催化作用", 《复旦学报(自然科学版)》 * |
| 李茸等: "表面活性改性剂对纳米NiB/SiO2粉体催化活性的影响", 《化学推进剂与高分子材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399525A (en) * | 2014-11-26 | 2015-03-11 | 上海大学 | Preparation method of hydrogenation catalyst for electrolytic liquidation of coal |
| CN104607192A (en) * | 2015-01-23 | 2015-05-13 | 上海大学 | Coal electrolysis hydro-liquefaction catalyst and preparation method thereof |
| CN110075852A (en) * | 2019-05-15 | 2019-08-02 | 武汉轻工大学 | A kind of preparation method of nanometer amorphous Ni-B catalyst |
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Application publication date: 20140101 |