CN104122128A - Aluminum oxide supported sulfurized molybdenum (tungsten) base hydrogenation catalyst activity phase sample preparing method - Google Patents
Aluminum oxide supported sulfurized molybdenum (tungsten) base hydrogenation catalyst activity phase sample preparing method Download PDFInfo
- Publication number
- CN104122128A CN104122128A CN201410349250.6A CN201410349250A CN104122128A CN 104122128 A CN104122128 A CN 104122128A CN 201410349250 A CN201410349250 A CN 201410349250A CN 104122128 A CN104122128 A CN 104122128A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- molybdenum disulfide
- reaction
- aluminum oxide
- centrifugal
- 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.)
- Granted
Links
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 10
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 title claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 65
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 36
- 238000005530 etching Methods 0.000 claims description 20
- 238000005464 sample preparation method Methods 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- HDJLCPMPTBFPCJ-UHFFFAOYSA-N [Mo].[W]=S Chemical compound [Mo].[W]=S HDJLCPMPTBFPCJ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004627 transmission electron microscopy Methods 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 2
- 238000001020 plasma etching Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 23
- DOIKGWMZXKJLJV-UHFFFAOYSA-N [W].[Mo](=S)=S Chemical compound [W].[Mo](=S)=S DOIKGWMZXKJLJV-UHFFFAOYSA-N 0.000 abstract description 17
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000011160 research Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000003486 chemical etching Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 101710116850 Molybdenum cofactor sulfurase 2 Proteins 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- -1 fluorine aluminium compound Chemical class 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
Abstract
The invention discloses an aluminum oxide supported sulfurized molybdenum (tungsten) base hydrogenation catalyst activity phase sample preparing method. According to the method, hydrofluoric acid is used as a chemical etchant and the use amount of the chemical etchant is 5-30 times stoichiometric amount of a catalyst-contained aluminum oxide supporter in total reaction; the time spent on reaction at normal temperature is 1-12 hours; a mixture system obtained from the reaction is subjected to the processes of specific centrifugation, supersonic vibration, ethanol-water exchange and the like so as to obtain a nanometer-scale molybdenum disulfide (tungsten) sample suspension which can be used for being observed by a transmission electron microscope. The sample preparing method is a universal sample preparing technology which is adopted when the microtopography of an aluminum oxide supported molybdenum disulfide (tungsten) catalyst hydrogenation activity phase is researched by virtue of the transmission electron microscope; by virtue of the technology, the contrast interference of the aluminum oxide supporter can be effectively eliminated, the statistics efficiency of observation on the molybdenum disulfide (tungsten) activity phase of a low-capacity catalyst is enhanced greatly, and therefore, key morphology parameters of projection, along the <001> direction, of a molybdenum disulfide (tungsten) nanometer particle can be obtained by virtue of the method.
Description
Technical field
The present invention relates to the sample preparation methods of a kind of alumina load molybdenum sulfide (tungsten) base activity of hydrocatalyst phase in petroleum refining industry, the method is at molybdenum disulfide (or the tungsten that uses transmission electron microscope to alumina load, or molybdenum, the two has concurrently tungsten) microscopic appearance of catalyst hydrogenation activity phase is while learning research, can adopt a kind of general sample preparation methods based on hydrofluorite chemical etching and subsequent treatment process, application the method can effectively be got rid of the contrast of alumina support and disturb, improve the active phase statistics efficiency of molybdenum disulfide and obtain the crucial pattern parameter of its <001> direction projection.
Background technology
For alumina load molybdenum disulfide (tungsten) class Hydrobon catalyst conventional in current domestic petroleum refining industry, the research of the active phase microscopic appearance of its molybdenum disulfide (tungsten) has the researching value of particular importance.The microstructural parameter (the stacking number of plies, platelet length, true profile etc.) that can effectively obtain the active phase of molybdenum disulfide (tungsten) becomes the important foundation of related industries Catalyst Design.
All the time, transmission electron microscope is the effective means of the active phase pattern of molybdenum disulfide (tungsten) research.But there is obviously limitation for the observation of the active phase of the molybdenum disulfide on alumina support (tungsten) in CEM.The one, due to the impact of the interference of carrier contrast, orientation problem and electron microscope operating parameter etc., only can obtain the microscopic appearance of the active phase of part molybdenum disulfide, molybdenum disulfide observation efficiency is lower than 10%; The 2nd, because carrier contrast is disturbed, molybdenum disulfide (tungsten) nano particle only can obtain two-dimensional projection's picture (obtaining structural parameters is the stacking number of plies, platelet length), and true profile profile and the defective bit etc. of the 3rd dimension of molybdenum disulfide (tungsten) particle (being <001> direction projection gained) cannot obtain all the time, this causes industrial molybdenum base activity of hydrocatalyst essence to carry out source problem and lacks all the time key evidence.
At present limited several acquisition support type molybdenum disulfide (tungsten) active phase topography research meanses (as annular dark, Three Dimensional Reconfiguration etc.) all need to use expensive specialized equipment, complicated operation and cannot investigate the catalyst sample that uses alumina support.If the contrast that can adopt certain means effectively to get rid of alumina support is disturbed, obtain the stabilising system of the active phase nano particle of pure molybdenum disulfide (tungsten), and use it for conventional transmission electron microscope research, will be expected to become the active phase research means of a kind of cheap, convenient, effective molybdenum disulfide (tungsten).
Summary of the invention
The applicant by correlative study and analyze find, consider from the principles of chemistry, alumina species has both sexes, can with strong acid or highly basic class substance reaction.Therefore, in use strong acid, highly basic class matter theory, say the system that realize complete reaction with alumina support and then obtain the active phase of pure molybdenum disulfide.But practical operation is got up, there is obvious deviation with theory in reality.Explore experiment early stage and show only to have hydrofluorite can obtain good etching effect as chemical etchant, gained suspension liquid cording has the operability of carrying out transmission electron microscope observing simultaneously.The practical application effect extreme difference of the etching agent such as hydrochloric acid, NaOH, long-time reaction also only has the etching efficiency that is no more than 20%, does not possess follow-up study completely and is worth.
Even if hydrofluorite is feasible as chemical etchant practical operation, still have many practical problemss to need to solve.One is the optimization of etching technics parameter, comprises the selection of consumption, reaction time, temperature of reaction of hydrofluorite etc.; The 2nd, the processing of hydrofluoric acid containing tail washings after etching, how to realize molybdenum disulfide (tungsten) nano particle and tail washings effective separation of (comprising the reaction product of unreacted hydrofluorite and hydrofluorite and aluminium oxide), both ensured that the active phase nano particle of molybdenum disulfide (tungsten) can not have loss along with this processing procedure, avoided again hydrofluorite and the interference of fluorine aluminium compound to transmission electron microscopy sample preparation process.
For this problem, the present invention proposes a kind of sample preparation methods that uses transmission electron microscope studying alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase, the chemical etching process conditions of hydrofluorite are optimized, adopt specific tail washings last handling process simultaneously, in the effective separation that ensures to have realized under the active prerequisite of not suffering a loss mutually of molybdenum disulfide tail washings, be convenient to the follow-up sample preparation for transmission electron microscope observing.
Based on above-mentioned research and experiment, the present invention proposes following technical scheme:
A kind of sample preparation methods of alumina load molybdenum sulfide (tungsten) base activity of hydrocatalyst phase, use hydrofluorite to mix with alumina load molybdenum sulfide (tungsten) base hydrogenation catalyst as chemical etchant, hydrofluorite consumption is 5-30 times of the contained alumina support total overall reaction of relative catalyzer stoichiometric amount, stirring and control the reaction time is 1-12 hour, and the mixture system obtaining after reaction obtains through centrifugal, ultrasonic concussion, alcohol-water exchange process the nanoscale molybdenum sulfide sample suspension of observing use as transmission electron microscopy.
Such scheme further comprises:
The mixture system treatment step obtaining after reaction is: first pass through centrifugal, cast out after supernatant and wash with deionized water, again centrifugal after sonic oscillation, cast out supernatant, repeat 2-3 time with this, all give up supernatant at every turn, in the centrifugal product that finally contains nanometer molybdenum sulfide at gained, add absolute ethyl alcohol, after sonic oscillation, obtain stable nano molybdenum disulfide-alcohol suspension.
Described hydrofluorite is the hydrofluoric acid aqueous solution of concentration 38-55%; Described centrifugal be centrifugal 10-20 minute under rotating speed 3000-10000 rev/min condition on supercentrifuge; Add sonic oscillation 10-30 minute after absolute ethyl alcohol.
Temperature of reaction is 35-45 DEG C, etching time 1-4 hour.
The method is in the time that the microscopic appearance of molybdenum disulfide (tungsten) the catalyst hydrogenation activity phase that uses transmission electron microscope to alumina load is learned research, the general sample preparation technology of one that can adopt, apply this technology and can effectively get rid of the contrast of alumina support and disturb, improve molybdenum disulfide (tungsten) active phase statistics efficiency and obtain the crucial pattern parameter of its <001> direction projection.Using transmission electron microscope studying alumina load molybdenum sulfide (tungsten) activity of hydrocatalyst phase time, the existence of alumina catalyst support tends to the microscopic appearance of molybdenum disulfide contained in catalyzer (tungsten) hydrogenation activity phase to observe and produce very serious negative influence, cause lower sample statistics efficiency, and the statistics rule larger with time of day deviation.
Embodiment
Below in conjunction with specific embodiment in detail technical scheme of the present invention and feature are described in detail:
Embodiment 1(is etching comparative example not)
Do not use the sample-pretreating method of hydrofluorite chemical etching, use the molybdenum disulfide/aluminium oxide catalyst (molybdenum disulfide charge capacity be 10%) of transmission electron microscope to low content of metal to carry out microscopic appearance research.In practical operation, find, under the contrast of alumina support is disturbed, be difficult to effectively observe the existence of the active phase nano particle of molybdenum disulfide, 20 photos are added up the molybdenum disulfide sample number obtaining lower than 150.The statistical research of pattern parameter distribution shows, the molybdenum disulfide relative content few (lower than 5%) of Monolayer Dispersion.
For the molybdenum sulfide/aluminium oxide catalyst (molybdenum disulfide charge capacity is 5%) of lower content of metal, through transmission electron microscope observing, result shows that now the contrast interference of alumina support is very serious, substantially cannot observe effective molybdenum disulfide sample.
Embodiment 2
This example is for the present invention's application hydrofluorite is as the embodiment of chemical etchant.Investigating object is still the molybdenum sulfide/aluminium oxide catalyst (molybdenum disulfide charge capacity is 10%) of the low content of metal in embodiment 1.
The concrete reaction conditions of hf etching is:
In plastic beaker, add approximately 0.3 gram of molybdenum disulfide/aluminium oxide catalyst sample (black), the hydrofluoric acid aqueous solution of 8 gram 47% and 20ml deionized water, under vigorous stirring state, room temperature reaction 8 hours, obtains a black suspension.This solution is moved in centrifuge tube, on supercentrifuge centrifugal 15 minutes (centrifuge speed 3000-10000 rev/min), cast out supernatant in pipe, add 5ml deionized water, the even black suspension of getting back after sonic oscillation, gives up supernatant after again centrifugal, and this step repeats 2-3 time altogether.In the centrifugal product finally obtaining, add 5ml absolute ethyl alcohol, within sonic oscillation 10-30 minute, obtain stable, a uniform black suspension.This suspending liquid liquid under static state can keep stablizing 2 hours above and do not occur obvious solid-liquid lamination.This molybdenum disulfide-alcohol suspension system can be used for follow-up transmission electron microscope observing.
The alcohol suspension of the nanometer MOS 2 particle of preparing with this sample treatment carries out sample preparation and passes through transmission electron microscope observing, EDX energy spectrometer shows that the relative content of aluminium oxide exceedes 400 lower than the molybdenum disulfide sample number that can add up in 0.5%, 20 photo.The statistical research of pattern parameter distribution shows, in the relative embodiment 1 of molybdenum disulfide relative content of Monolayer Dispersion, etching sample has not had obvious increase (approaching 15%).This shows the sample pre-treatments preparation means that adopts hydrofluorite chemical etching to use transmission electron microscope microscopic appearance to observe as alumina load molybdenum disulfide hydrogenation catalyst, alumina support disturbs effectively to be got rid of, obtained higher statistical efficiency, the active phase statistical distribution of the molybdenum disulfide rule simultaneously obtaining more approaches time of day.And likely cause this catalyzer microscopic appearance research to obtain wrong conclusion without the transmission electron microscope results of the sample of over etching processing.
Embodiment 3
In this example, change the temperature of reaction of hydrofluorite chemical etching.Hydrofluorite chemical etching reaction conditions is basic consistent with embodiment 2, only temperature of reaction is changed to 40 DEG C by normal temperature.Etching rate testing result shows, uses the thermal rection condition that adds in certain limit, and the etch rate of alumina support can significantly improve, and can foreshorten to 2 hours by 8-10 hour, and alumina support etching rate reaches more than 99%.Meanwhile, the microscopic appearance of the active phase of molybdenum disulfide obtaining after etching is through transmission electron microscope observing, and the relative embodiment 2 of statistics rule of its pattern parameter has no obviously and departs from.
Embodiment 4(salt acid etch comparative example)
Adopt the catalyzer object investigated in embodiment 2 and with the similar reaction conditions of hydrofluorite, only changing chemical etchant is hydrochloric acid.Practical operation finds, though hydrochloric acid consumption reach with catalyzer in alumina support complete reaction stoichiometry 30-60 doubly, the reaction time is 8 hours, the etching efficiency of alumina support only has 17.5%.And hydrochloric acid consumption is less, etching efficiency is lower.And continue to strengthen hydrochloric acid consumption, in the same time, etching rate is no more than 20%.
Embodiment 5(NaOH etching comparative example)
Adopt the catalyzer object investigated in embodiment 2 and with the similar reaction conditions of hydrofluorite, only changing chemical etchant is NaOH.Practical operation finds, though sodium hydroxide concentration reach with catalyzer in alumina support complete reaction stoichiometry 15-60 doubly, the reaction time is 8 hours, the etching efficiency of alumina support is no more than 8%.Continue to increase sodium hydroxide concentration, can be because system viscosity is excessive, cause post-processing step effectively to carry out.
Embodiment 6
This example is for application hydrofluorite is as the embodiment of chemical etchant.Investigate the sulphided state tungsten disulfide/aluminium oxide catalyst (tungsten disulfide charge capacity is 10%) of the low content of metal of object.
The concrete reaction conditions of hf etching and post-treatment condition all with embodiment 2 are consistent as investigating when object taking molybdenum disulfide catalyst.Finally can obtain equally stable, a uniform black suspension.This suspending liquid can under static state keep stablizing 2 hours above and do not occur obvious solid-liquid lamination.This tungsten disulfide-alcohol suspension system can be used for follow-up transmission electron microscope observing.
The alcohol suspension of the Wolfram disulfide nano particle of preparing with this sample-pretreating method carries out sample preparation and passes through transmission electron microscope observing, EDX energy spectrometer shows that the relative content of aluminium oxide exceedes 400 lower than the molybdenum disulfide sample number that can add up in 0.4%, 20 photo.Sample pre-treatments preparation means when this shows to adopt hydrofluorite chemical etching to can be used as equally alumina load tungsten disulfide activity of hydrocatalyst to use mutually transmission electron microscope to carry out microscopic appearance research, alumina support disturbs and can effectively be got rid of, and has obtained higher statistical efficiency.
Comprehensive above embodiment comparative analysis, in the time using conventional transmission electron microscope to be applied to sulphided state molybdenum (tungsten) the base activity of hydrocatalyst phase topography research of alumina load, the contrast serious interference of alumina support affects active phase topography statistical efficiency, and statistical law easy and time of day generation relatively large deviation in the time of low charge capacity.The present invention has designed the sample preparation methods of a kind of use transmission electron microscope studying alumina load molybdenum disulfide (tungsten) base activity of hydrocatalyst phase, the method is in the time that the microscopic appearance of the molybdenum disulfide catalyst hydrogenation activity phase that uses transmission electron microscope to alumina load is learned research, apply this technology and can effectively get rid of the contrast interference of alumina support, can improve nearly 3 times to the active phase statistics of the molybdenum disulfide of low charge capacity catalyst system efficiency, obtain the pattern parameter distribution rule that more approaches time of day.Especially, can obtain the crucial pattern parameter of molybdenum disulfide (tungsten) nano particle along <001> direction projection by the method, for the element tasks such as this area inner catalyst research and development provide crucial foundation.
Claims (4)
1. the sample preparation methods of an alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase, it is characterized in that using hydrofluorite to mix with alumina load molybdenum sulfide (tungsten) base hydrogenation catalyst as chemical etchant, hydrofluorite consumption is 5-30 times of the contained alumina support total overall reaction of relative catalyzer stoichiometric amount, stirring and control the reaction time is 1-12 hour, and the mixture system obtaining after reaction obtains through centrifugal, ultrasonic concussion, alcohol-water exchange process the nanoscale molybdenum sulfide sample suspension of observing use as transmission electron microscopy.
2. the sample preparation methods of alumina load molybdenum sulfide according to claim 1 (tungsten) base activity of hydrocatalyst phase, it is characterized in that the mixture system treatment step obtaining after reactive ion etching is: first pass through centrifugal, cast out after supernatant and wash with deionized water, again centrifugal after sonic oscillation, cast out supernatant, repeat 2-3 time with this, all give up supernatant at every turn, in the last centrifugal product that contains nanometer molybdenum sulfide at gained, add absolute ethyl alcohol, after sonic oscillation, obtain stable nano molybdenum disulfide-alcohol suspension.
3. the sample preparation methods of alumina load molybdenum sulfide according to claim 2 (tungsten) base activity of hydrocatalyst phase, is characterized in that described hydrofluorite is the hydrofluoric acid aqueous solution of concentration 38-55%; Described centrifugal be centrifugal 10-20 minute under rotating speed 3000-10000 rev/min condition on supercentrifuge; Add sonic oscillation 10-30 minute after absolute ethyl alcohol.
4. according to the sample preparation methods of alumina load molybdenum sulfide (tungsten) the base activity of hydrocatalyst phase described in claim 1 or 2,3, it is characterized in that temperature of reaction is 35-45 DEG C, etching time 1-4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410349250.6A CN104122128B (en) | 2014-07-22 | 2014-07-22 | A kind of sample preparation methods of alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410349250.6A CN104122128B (en) | 2014-07-22 | 2014-07-22 | A kind of sample preparation methods of alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104122128A true CN104122128A (en) | 2014-10-29 |
| CN104122128B CN104122128B (en) | 2016-04-20 |
Family
ID=51767629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410349250.6A Active CN104122128B (en) | 2014-07-22 | 2014-07-22 | A kind of sample preparation methods of alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104122128B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862387A (en) * | 2018-05-30 | 2018-11-23 | 中国石油大学(华东) | A kind of preparation method of abnormity nano molybdenum disulfide material |
| CN110368934A (en) * | 2019-08-15 | 2019-10-25 | 安徽元琛环保科技股份有限公司 | A kind of preparation method of wire mesh SCR denitration and catalyst obtained |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049800A (en) * | 1989-08-28 | 1991-03-13 | 中国石油化工总公司石油化工科学研究院 | The preparation of nickel/aluminium oxide catalyst |
| CN1266085A (en) * | 2000-02-03 | 2000-09-13 | 中国石油天然气股份有限公司兰州石化分公司 | Selective hydrogenation catalyst for pyrolysis gasoline |
| JP2010536572A (en) * | 2007-08-30 | 2010-12-02 | ソルヴェイ（ソシエテ アノニム） | Catalyst support and preparation method thereof |
| US20100317910A1 (en) * | 2009-06-12 | 2010-12-16 | Albemarle Europe Sprl | Sapo molecular sieve catalysts and their preparation and uses |
| CN102443431A (en) * | 2010-10-13 | 2012-05-09 | 天津河清化学工业有限公司 | Naphtha hydrorefining dearomatization method |
-
2014
- 2014-07-22 CN CN201410349250.6A patent/CN104122128B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049800A (en) * | 1989-08-28 | 1991-03-13 | 中国石油化工总公司石油化工科学研究院 | The preparation of nickel/aluminium oxide catalyst |
| CN1266085A (en) * | 2000-02-03 | 2000-09-13 | 中国石油天然气股份有限公司兰州石化分公司 | Selective hydrogenation catalyst for pyrolysis gasoline |
| JP2010536572A (en) * | 2007-08-30 | 2010-12-02 | ソルヴェイ（ソシエテ アノニム） | Catalyst support and preparation method thereof |
| US20100317910A1 (en) * | 2009-06-12 | 2010-12-16 | Albemarle Europe Sprl | Sapo molecular sieve catalysts and their preparation and uses |
| CN102443431A (en) * | 2010-10-13 | 2012-05-09 | 天津河清化学工业有限公司 | Naphtha hydrorefining dearomatization method |
Non-Patent Citations (2)
| Title |
|---|
| 柴永明 等: "过渡金属硫化物催化剂催化加氢作用机理", 《化学进展》 * |
| 肖进兵 等: "氧化铝负载氮化钼的表面性质及加氢脱氢性能", 《催化学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862387A (en) * | 2018-05-30 | 2018-11-23 | 中国石油大学(华东) | A kind of preparation method of abnormity nano molybdenum disulfide material |
| CN110368934A (en) * | 2019-08-15 | 2019-10-25 | 安徽元琛环保科技股份有限公司 | A kind of preparation method of wire mesh SCR denitration and catalyst obtained |
| CN110368934B (en) * | 2019-08-15 | 2022-08-09 | 安徽元琛环保科技股份有限公司 | Preparation method of wire mesh SCR denitration catalyst and prepared catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104122128B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104439279B (en) | A kind of method realizing regulation and control nano silver wire diameter by sodium chloride consumption | |
| Shi et al. | Controlled fabrication of photoactive copper oxide–cobalt oxide nanowire heterostructures for efficient phenol photodegradation | |
| CN103613136A (en) | Preparation method of square MoO3 nanosheet | |
| CN105417524B (en) | A kind of preparation method of the mesoporous graphene of the controllable thickness of high-sequential | |
| CN102631910B (en) | Stable graphene/titanium oxide composite nanosol and preparation method thereof | |
| CN102879430B (en) | Graphene/polyaniline hybrid material-based gas sensor and preparation method for same | |
| US11512000B2 (en) | Porous graphene film, its manufacturing method and electronic product | |
| CN104900867A (en) | Preparation method of CNT/Co/MoS2 composite material | |
| EP3620437A1 (en) | Linear hierarchical structure lithium titanate material, preparation and application thereof | |
| CN108439470A (en) | A kind of preparation method and application of molybdenum disulfide nano sheet | |
| CN105006376B (en) | A kind of preparation method of carbon nanotube and nickel oxide composite material | |
| CN108483502A (en) | A kind of preparation method and application of rhenium disulfide nanometer sheet | |
| Li et al. | Template-free synthesis of uniform mesoporous SnO2 nanospheres for efficient phosphopeptide enrichment | |
| CN104174414B (en) | A kind of molybdenum bisuphide/titanium dioxide compound and preparation method thereof | |
| CN104122128A (en) | Aluminum oxide supported sulfurized molybdenum (tungsten) base hydrogenation catalyst activity phase sample preparing method | |
| CN103420362A (en) | Preparation method for graphene | |
| CN105129849A (en) | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof | |
| CN104402047A (en) | Method for preparing exposed crystal face controllable rutile-type TiO2 nanorod self-assembling microspheres | |
| CN101736332B (en) | Method for synthesizing amorphous nickel-cobalt alloy nano-film loaded with platinum particles | |
| Karim et al. | A contemplating review on different synthesis methods of 2D-Molybdenum disulfide (MoS2) nanosheets | |
| Xue et al. | Tailoring the surface morphology of TiO2 nanotube arrays connected with nanowires by anodization | |
| US11505465B2 (en) | Method of obtainment of nanomaterials composed of carbonaceous material and metal oxides | |
| CN108726548B (en) | Method for preparing hollow nano aluminum oxide from surface-passivated nano aluminum | |
| CN104445318B (en) | A kind of sea urchin shape aluminum oxyhydroxide ball and preparation method thereof | |
| CN109437260A (en) | A kind of rapid precipitation prepares one-dimensional Mg (OH)2Method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201126 Address after: 257000 No.65 Guangkai Road, Guangrao Economic Development Zone, Guangrao County, Dongying City, Shandong Province Patentee after: Shandong Hepeng Technology Co.,Ltd. Patentee after: CHINA University OF PETROLEUM (EAST CHINA) Address before: 266580 China University of Petroleum, 66 West Changjiang Road, Qingdao economic and Technological Development Zone, Shandong (Hua Dong) Patentee before: China University of Petroleum (East China) |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240119 Address after: 266580 China University of petroleum, 66 Changjiang West Road, Qingdao Economic and Technological Development Zone, Shandong Province (East China) Patentee after: CHINA University OF PETROLEUM (EAST CHINA) Address before: 257000 No.65 Guangkai Road, Guangrao Economic Development Zone, Guangrao County, Dongying City, Shandong Province Patentee before: Shandong Hepeng Technology Co.,Ltd. Patentee before: CHINA University OF PETROLEUM (EAST CHINA) |