CN104122128B - A kind of sample preparation methods of alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase - Google Patents
A kind of sample preparation methods of alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 238000005464 sample preparation method Methods 0.000 title claims abstract description 12
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 37
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 28
- 238000005530 etching Methods 0.000 claims description 19
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000004627 transmission electron microscopy Methods 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
- 238000005266 casting Methods 0.000 claims description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 claims 1
- 238000001020 plasma etching Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 22
- DOIKGWMZXKJLJV-UHFFFAOYSA-N [W].[Mo](=S)=S Chemical compound [W].[Mo](=S)=S DOIKGWMZXKJLJV-UHFFFAOYSA-N 0.000 abstract description 19
- 238000011160 research Methods 0.000 abstract description 15
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000003486 chemical etching Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- HDJLCPMPTBFPCJ-UHFFFAOYSA-N [Mo].[W]=S Chemical compound [Mo].[W]=S HDJLCPMPTBFPCJ-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000006185 dispersion Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 fluorine aluminium compound Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing 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
- RVGWKSDRTRBKLB-UHFFFAOYSA-N [Mo](=S)=S.C(C)O Chemical class [Mo](=S)=S.C(C)O RVGWKSDRTRBKLB-UHFFFAOYSA-N 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
- 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
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Abstract
A kind of sample preparation methods of alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase, use hydrofluorite as chemical etchant, the 5-30 of hydrofluorite consumption alumina support total overall reaction stoichiometric amount contained by relative catalyst doubly, reaction time is 1-12 hour under normal temperature, and the mixture system obtained after reaction obtains nanoscale molybdenum disulfide (tungsten) the sample suspension that can be used as transmission electron microscope observing through processes such as specifically centrifugal, ultrasonic vibration, alcohol-water exchanges.The method is when the microscopic appearance research using transmission electron microscope to molybdenum disulfide (tungsten) the catalyst hydrogenation activity phase of alumina load; a kind of universal sample technology of preparing adopted; apply the contrast interference that this technology effectively can get rid of alumina support; significantly improve the statistics efficiency that low charge capacity catalyzer molybdenum disulfide (tungsten) activity is observed mutually, and molybdenum disulfide (tungsten) nano particle can be obtained whereby along & lt; 001 & gt; The crucial structural parameters of direction projection.
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 using transmission electron microscope to the molybdenum disulfide of alumina load (or tungsten, or molybdenum, both tungsten has concurrently) research of the microscopic appearance of catalyst hydrogenation activity phase time, a kind of universal sample preparation method based on hydrofluorite chemical etching and subsequent treatment process can be adopted, application the method effectively can get rid of the contrast interference of alumina support, improve the active phase statistics efficiency of molybdenum disulfide and obtain the crucial structural parameters 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 effectively can obtain molybdenum disulfide (tungsten) active phase becomes the important foundation of related industries Catalyst Design.
All the time, transmission electron microscope is the most effective means of molybdenum disulfide (tungsten) active phase morphology research.But there is obviously limitation for the observation of molybdenum disulfide (tungsten) the active phase on alumina support in CEM.One is the impact due to the interference of carrier contrast, orientation problem and electron microscope operating parameter etc., and only can obtain the microscopic appearance of the active phase of part molybdenum disulfide, molybdenum disulfide observation efficiency is lower than 10%; Two is due to the interference of carrier contrast, 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 the actual profile profile of molybdenum disulfide (tungsten) particle the 3rd dimension (i.e. <001> direction projection gained) and defective bit etc. cannot obtain all the time, this causes industrial molybdenum base activity of hydrocatalyst essence to carry out source problem and lacks key evidence all the time.
The active phase morphology research means (as annular dark, Three Dimensional Reconfiguration etc.) of several acquisition support type molybdenum disulfide (tungsten) limited at present all needs to use expensive specialized equipment, complicated operation and cannot investigate the catalyst sample using alumina support.If certain means can be adopted effectively to get rid of the contrast interference of alumina support, obtain the stabilising system of the active phase nano particle of pure molybdenum disulfide (tungsten), and use it for conventional transmission electron microscopy study, 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, chemically principle is considered, alumina species has both sexes, can with strong acid or highly basic class substance reaction.Therefore, system strong acid, highly basic class matter theory said and realize complete reaction with alumina support and then obtain the active phase of pure molybdenum disulfide is used.But practical operation is got up, there is obvious deviation in reality and theory.Early stage, explorative experiment showed only have hydrofluorite can obtain good etching effect as chemical etchant, and 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 being no more than 20%, does not possess follow-up study completely and is worth.
Even if hydrofluorite is feasible as chemical etchant practical operation, many practical problemss are still had to need to solve.One is the optimization of etch process parameters, comprises the selection of the consumption of hydrofluorite, reaction time, temperature of reaction etc.; Two is the process etching rear hydrofluoric acid containing tail washings, how to realize effective separation of molybdenum disulfide (tungsten) nano particle and tail washings (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, and avoided again hydrofluorite and fluorine aluminium compound to the interference of transmission electron microscopy sample preparation process.
For this problem, the present invention proposes a kind of sample preparation methods using transmission electron microscope studying alumina load sulphided state molybdenum (tungsten) base activity of hydrocatalyst phase, optimize the chemical etching process condition of hydrofluorite, adopt specific tail washings last handling process simultaneously, ensureing the effective separation achieving tail washings under the active prerequisite of not suffering a loss mutually of molybdenum disulfide, 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, hydrofluorite is used to mix with alumina load molybdenum sulfide (tungsten) base hydrogenation catalyst as chemical etchant, the 5-30 of hydrofluorite consumption alumina support total overall reaction stoichiometric amount contained by relative catalyst doubly, stirring and controlling the reaction time is 1-12 hour, and the mixture system obtained after reaction obtains through centrifugal, ultrasonic vibration, alcohol-water exchange process the nanoscale molybdenum sulfide sample suspension being used as Transmission electron microscopy.
Such scheme comprises further:
The mixture system treatment step obtained after reaction is: first through centrifugal, deionized water is spent after casting out supernatant, again centrifugal after sonic oscillation, cast out supernatant, repeat 2-3 time with this, all give up supernatant at every turn, finally contain at gained in the centrifugal product of nanometer molybdenum sulfide and 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 when the microscopic appearance research using transmission electron microscope to molybdenum disulfide (tungsten) the catalyst hydrogenation activity phase of alumina load, a kind of universal sample technology of preparing that can adopt, apply the contrast interference that this technology effectively can get rid of alumina support, improve molybdenum disulfide (tungsten) active phase statistics efficiency and obtain the crucial structural parameters of its <001> direction projection.At use transmission electron microscope studying alumina load molybdenum sulfide (tungsten) activity of hydrocatalyst phase time, the existence of alumina catalyst support is often observed the microscopic appearance of molybdenum disulfide (tungsten) hydrogenation activity phase contained in catalyzer and is produced 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(does not etch comparative example)
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.Find in practical operation, under the contrast interference of alumina support, be difficult to the existence effectively observing the active phase nano particle of molybdenum disulfide, the molybdenum disulfide sample number that 20 photos are added up to obtain is lower than 150.The statistical research of structural parameters 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 the contrast interference of now 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 about 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), casts out supernatant in pipe, add 5ml deionized water, get back after sonic oscillation a homogeneous black suspension, give up supernatant after again centrifugal, this step repeats 2-3 time altogether.Add 5ml absolute ethyl alcohol in the centrifugal product finally obtained, within sonic oscillation 10-30 minute, obtain stable, a uniform black suspension.This suspending liquid liquid under static state can keep stablizing more than 2 hours and not occurring obvious solid-liquid lamination.This molybdenum disulfide-ethanol suspension liquid system can be used for follow-up transmission electron microscope observing.
The alcohol suspension of the nanometer MOS 2 particle prepared with this sample treatment carries out sample preparation and passes through transmission electron microscope observing, the relative content of EDX energy spectrometer display aluminium oxide is lower than 0.5%, and the molybdenum disulfide sample number can added up in 20 photos is more than 400.The statistical research of structural parameters distribution shows, the molybdenum disulfide relative content of Monolayer Dispersion has had obvious increase (close to 15%) relative to not etching sample in embodiment 1.This shows the sample pre-treatments preparation means adopting hydrofluorite chemical etching to use transmission electron microscope microscopic appearance to observe as alumina load molybdenum disulfide hydrogenation catalyst, alumina support interference is effectively got rid of, obtain higher statistical efficiency, the molybdenum disulfide simultaneously obtained active phase statistical distribution rule is closer to time of day.And likely cause without the transmission electron microscope results of the sample of etching processing the conclusion research of this catalyzer microscopic appearance being obtained to mistake.
Embodiment 3
The temperature of reaction of hydrofluorite chemical etching is have changed in this example.Hydrofluorite chemistry etching reaction condition 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 to add thermal rection condition 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 the molybdenum disulfide obtained after etching is through transmission electron microscope observing, and the relative embodiment 2 of statistics rule of its structural parameters has no and obviously departs from.
Embodiment 4(salt acid etch comparative example)
Adopt the catalyzer object and the reaction conditions similar with hydrofluorite investigated in embodiment 2, only changing chemical etchant is hydrochloric acid.Practical operation finds, even if hydrochloric acid consumption reaches and the 30-60 of alumina support complete reaction stoichiometry in catalyzer times, the reaction time is 8 hours, and 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 and the reaction conditions similar with hydrofluorite investigated in embodiment 2, only changing chemical etchant is NaOH.Practical operation finds, even if sodium hydroxide concentration reaches and the 15-60 of alumina support complete reaction stoichiometry in catalyzer times, the reaction time is 8 hours, and the etching efficiency of alumina support is no more than 8%.Continue to increase sodium hydroxide concentration, then can be excessive due to system viscosity, 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 in be investigate object with molybdenum disulfide catalyst time be consistent.Finally can obtain stable, a uniform black suspension equally.This suspending liquid can under static state keep stablizing more than 2 hours and not occurring obvious solid-liquid lamination.This tungsten disulfide-ethanol suspension liquid system can be used for follow-up transmission electron microscope observing.
The alcohol suspension of the Wolfram disulfide nano particle prepared with this sample-pretreating method carries out sample preparation and passes through transmission electron microscope observing, the relative content of EDX energy spectrometer display aluminium oxide is lower than 0.4%, and the molybdenum disulfide sample number can added up in 20 photos is more than 400.Sample pre-treatments preparation means when this shows to adopt hydrofluorite chemical etching transmission electron microscope can be used mutually to carry out microscopic appearance research as alumina load tungsten disulfide activity of hydrocatalyst equally, alumina support interference can effectively be got rid of, and obtains higher statistical efficiency.
Comprehensive above embodiment comparative analysis, when using conventional transmission Electronic Speculum to be applied to sulphided state molybdenum (tungsten) the base activity of hydrocatalyst phase morphology research of alumina load, the contrast serious interference of alumina support affects active phase morphology statistical efficiency, and statistical law when low charge capacity easily and time of day produce relatively large deviation.The present invention devises a kind of sample preparation methods using transmission electron microscope studying alumina load molybdenum disulfide (tungsten) base activity of hydrocatalyst phase, the method is when the microscopic appearance research using transmission electron microscope to the molybdenum disulfide catalyst hydrogenation activity phase of alumina load, apply the contrast interference that this technology effectively can get rid of alumina support, nearly 3 times can be improved to the molybdenum disulfide active phase statistics efficiency of low charge capacity catalyst system, obtain the structural parameters regularity of distribution closer to time of day.Especially, the crucial structural parameters of molybdenum disulfide (tungsten) nano particle along <001> direction projection can be obtained 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 molybdenum sulfide base or tungsten sulfide base activity of hydrocatalyst phase, it is characterized in that using hydrofluorite to mix with alumina load molybdenum sulfide base or tungsten sulfide base hydrogenation catalyst as chemical etchant, the 5-30 of hydrofluorite consumption alumina support total overall reaction stoichiometric amount contained by relative catalyst doubly, stirring and controlling the reaction time is 1-12 hour, the mixture system obtained after reaction is through centrifugal, ultrasonic vibration, alcohol-water exchange process obtains the nanoscale molybdenum disulfide or nanoscale tungsten disulfide sample suspension that are used as Transmission electron microscopy.
2. the sample preparation methods of alumina load molybdenum sulfide base according to claim 1 or tungsten sulfide base activity of hydrocatalyst phase, the mixture system treatment step obtained after it is characterized in that reactive ion etching is: first through centrifugal, deionized water is spent after casting out supernatant, again centrifugal after sonic oscillation, cast out supernatant, repeat 2-3 time with this, all give up supernatant at every turn, absolute ethyl alcohol is added in the centrifugal product finally containing nanoscale molybdenum disulfide or nanoscale tungsten disulfide at gained, stable nanoscale molybdenum disulfide-alcohol suspension or nanoscale tungsten disulfide-alcohol suspension is obtained after sonic oscillation.
3. the sample preparation methods of alumina load molybdenum sulfide base according to claim 2 or tungsten sulfide 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. the sample preparation methods of the alumina load molybdenum sulfide base according to claim 1 or 2 or 3 or tungsten sulfide base activity of hydrocatalyst phase, is characterized in that temperature of reaction is 35-45 DEG C, etching time 1-4 hour.
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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) |
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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) |