CN1323756C - Method for preparing nanometer molybdenum carbide/aluminium sesquioxide compounding catalyst - Google Patents
Method for preparing nanometer molybdenum carbide/aluminium sesquioxide compounding catalyst Download PDFInfo
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- CN1323756C CN1323756C CNB2005100623003A CN200510062300A CN1323756C CN 1323756 C CN1323756 C CN 1323756C CN B2005100623003 A CNB2005100623003 A CN B2005100623003A CN 200510062300 A CN200510062300 A CN 200510062300A CN 1323756 C CN1323756 C CN 1323756C
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- ball milling
- molybdenum carbide
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000013329 compounding Methods 0.000 title claims description 6
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title abstract description 24
- 229910039444 MoC Inorganic materials 0.000 title abstract description 24
- 238000000034 method Methods 0.000 title abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000004411 aluminium Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 6
- 235000016768 molybdenum Nutrition 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HOOANQZZUGPTRH-UHFFFAOYSA-N molybdenum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mo+3].[Mo+3] HOOANQZZUGPTRH-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Abstract
The present invention discloses a preparation method for a nanometer molybdenum carbide/ alundum composite catalyst. Ball milling is carried out to molybdenum trioxide powder, aluminium powder and graphite powder in the atomic ratio of 1: 2: 0.8-2; the mass ratio of ball powder is 20-40: 1; the rotation speed of a ball mill is from 250 to 400 rpm; the time of the ball milling is from 70 to 120 hours; calcination is carried out in the air to remove residual graphitic carbon, and the temperature of the calcination is from 430 to 550DEG. C; the composite catalyst powder is obtained. Compared with other methods, the present invention has the following advantages that the prepared composite catalyst of molybdenum carbide is uniformly dispersed in alundum, the crystal particles of composite material is in a nanometer stage, the method of the ball milling is used, the required chemical agents are fewer, the device and the manufacturing process are simple, the production cost is low, and compared with the existing method, no noxious gas such as carbon monoxide, etc. is produced in the technological process, and the present invention has no harm to the environment.
Description
Technical field
The present invention relates to field of material preparation, relate in particular to a kind of preparation method of nano silicon carbide molybdenum/aluminium sesquioxide compounding catalyst.
Background technology
Rare precious metals such as platinum group metal or VIII group 4 transition metal, especially platinum, palladium, rhodium, iridium, ruthenium are widely used in chemical industry fields such as chemical synthesis, petrochemical industry and environmental protection usually as catalyst.But this metalloid, especially some rare precious metals, limited because of its reserves, along with the continuous increase to their demands, people wish to find other materials with similar catalysis and acquisition easily to substitute them.Molybdenum carbide (β-Mo
2C) because of its special structure has the electronic structure similar to noble metal, thus make have in its a lot of chemical reactions with precious metal like catalytic performance.There are some researches show that molybdenum carbide has good catalytic activity for hydrodesulfurization reaction, hydrodenitrogeneration reaction, isomerization reaction and the hydrocarbon conversion and synthetic reaction, molybdenum carbide is for the anti-poisoning performance of the sulphur that produces in the desulphurization reaction simultaneously.Along with going deep into of research, carbide such as molybdenum carbide are expected to become the new catalyst that substitutes rare precious metals.
Based on the good prospect of molybdenum carbide as catalyst, developed the multiple method for preparing molybdenum carbide at present, mainly comprise temperature-programmed reduction method, vapor phase method and thermal decomposition method.These methods generally all will adopt presoma or the compound that contains molybdenum, at high temperature chemical reaction and make molybdenum carbide.The equipment complexity that adopts can produce pernicious gases such as carbon monoxide in the technical process.Molybdenum carbide generally need be dispersed in when practical application in the carrier (normally alundum (Al) and use simultaneously, and how the molybdenum carbide that makes being evenly dispersed in the carrier is that these class methods prepare the problem that molybdenum carbide catalyst need solve.How preparing molybdenum carbide cheaply, simultaneously itself and carrier are disperseed equably, is must solve the ground problem in the practical application.
Ball milling is a kind of simple lower cost materials preparation method.Utilize mechanico-chemical reaction to prepare nano material by ball milling wide application prospect is arranged.Each component of composite of this method preparation is uniformly dispersed, and specific area is big, and the crystal grain of each phase of material is nanoscale simultaneously.Utilize ball milling to prepare molybdenum carbide/Al 2 O 3 composition, effectively workout cost and dispersed problem have very strong practical value.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of molybdenum carbide/aluminium sesquioxide compounding catalyst.
It is that molybdenum trioxide powder, aluminium powder and graphite powder are carried out ball milling with the ratio of atomic ratio 1: 2: 0.8～2, ball material mass ratio is 20～40: 1, drum's speed of rotation is 250～400rpm, the ball milling time is 70～120 hours, calcining is to remove remaining free carbon in air, calcining heat is 430～550 ℃, obtains the composite catalyst powder.
Described molybdenum trioxide powder, aluminium powder and graphite powder are 1: 2: 1～1.5 for good with atomic ratio
Compare with additive method, the present invention has following advantage: (1) makes the composite catalyst molybdenum carbide and is uniformly dispersed in alundum (Al, and the crystal grain of composite is nanoscale.(2) means of employing ball milling, required chemical reagent is less, and apparatus and process is simple, and production cost is low.(3) compare with existing method, can not produce in this technical process, environment is not had harm as toxic gases such as carbon monoxide.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of final composite catalyst powder in the embodiment of the invention 1;
Fig. 2 is the X ray diffracting spectrum of final composite catalyst powder in the embodiment of the invention 2.
The specific embodiment
The present invention utilizes mechanico-chemical reaction to generate the composite of molybdenum carbide and alundum (Al, and molybdenum carbide is good dispersion in alundum (Al, and the crystal grain of material is nanoscale.
The consumption of the present invention's graphite powder under identical ball milling condition had a significant impact the required ball milling time, and in order to obtain pure composite catalyst in the short period relatively, the consumption of graphite powder generally will be higher than the consumption of the required graphite powder of reaction ratio.Remaining free carbon can be removed by calcining at a certain temperature, and catalyst can keep stable under this temperature.
Abrading-ball and ball grinder that ball milling uses are stainless steel material.The diameter of abrading-ball is 4～18mm, adopts the ball of different-diameter to be used during ball milling.
Because have molybdenum to be come out by aluminium reducing in the mechanico-chemical reaction process, the molybdenum that restores under this state is oxidized easily.In order to prevent oxidation, when carrying out ball milling, after abrading-ball and raw material were put into ball grinder, the reply ball grinder vacuumized, and general vacuum is 0.1～2Pa.After vacuumizing, also should charge into inert gas shielding.The inert gas that charges into is generally high-purity argon gas, and the pressure that charges into gas is 0.1～2MPa.
Take by weighing 6.86 gram molybdenum trioxide powder, 2.57 gram aluminium powders and 0.57 gram graphite powder and put into the stainless-steel vacuum ball grinder, add 200 gram stainless steel abrading-balls.Seal charging door, be evacuated to 0.4Pa, pour argon shield, pressure is 0.18MPa, places ball milling on the ball mill, and drum's speed of rotation is 300rpm.Behind the ball milling 100 hours, open ball grinder and take out powder sample, in tube furnace, remove free carbon in 500 ℃ of calcinings.Fig. 1 is the X-ray diffractogram of end product.As can be seen from the figure, end product has only alundum (Al and molybdenum carbide.And the crystal grain that calculates molybdenum carbide according to the Scherrer formula is about 30 nanometers.
Take by weighing 6.94 gram molybdenum trioxide powder, 2.60 gram aluminium powders and 0.46 gram graphite powder and put into the stainless-steel vacuum ball grinder, add 400 gram stainless steel abrading-balls.Seal charging door, be evacuated to 0.6Pa, pour argon shield, pressure is 0.15MPa, places ball milling on the ball mill, and drum's speed of rotation is 350rpm.Behind the ball milling 120 hours, open ball grinder and take out powder sample, in tube furnace, remove free carbon in 430 ℃ of calcinings.End product is alundum (Al and molybdenum carbide composite granule.
Embodiment 3
Take by weighing 6.66 gram molybdenum trioxide powder, 2.49 gram aluminium powders and 0.85 gram graphite powder and put into the stainless-steel vacuum ball grinder, add 300 gram stainless steel abrading-balls.Seal charging door, be evacuated to 0.7Pa, pour argon shield, pressure is 0.17MPa, places ball milling on the ball mill, and drum's speed of rotation is 250rpm.Behind the ball milling 80 hours, open ball grinder and take out powder sample, in tube furnace, remove free carbon in 500 ℃ of calcinings.End product is alundum (Al and molybdenum carbide composite granule.
Embodiment 4
Take by weighing 6.49 gram molybdenum trioxide powder, 2.43 gram aluminium powders and 1.08 gram graphite powders and put into the stainless-steel vacuum ball grinder, add 200 gram stainless steel abrading-balls.Seal charging door, be evacuated to 0.9Pa, pour argon shield, pressure is 0.16MPa, places ball milling on the ball mill, and drum's speed of rotation is 250rpm.Behind the ball milling 70 hours, open ball grinder and take out powder sample, in tube furnace, remove free carbon in 550 ℃ of calcinings.End product is alundum (Al and molybdenum carbide composite granule.
Embodiment 5
For the influence to the required ball milling time under the same terms of content that graphite powder is described, present embodiment and embodiment 1 contrast, and the graphite powder consumption of taking is a chemical reaction proportioning institute expense.Take by weighing 7.06 gram molybdenum trioxide powder, 2.64 gram aluminium powders and 0.3 gram graphite powder and put into the stainless-steel vacuum ball grinder, add 200 gram stainless steel abrading-balls.Seal charging door, be evacuated to 0.4Pa, pour argon shield, pressure is 0.18MPa, places ball milling on the ball mill, and drum's speed of rotation is 300rpm.Behind the ball milling 150 hours, open ball grinder and take out powder sample.Fig. 2 shows in the product except alundum (Al to have only a spot of molybdenum sesquioxide to generate, and still has a large amount of molybdenums to exist.This shows and will obtain pure composite catalyst powder in the short relatively time that graphite powder must be excessive.
Claims (2)
1. the preparation method of a nano silicon carbide molybdenum/aluminium sesquioxide compounding catalyst, it is characterized in that: molybdenum trioxide powder, aluminium powder and graphite powder are carried out ball milling with the ratio of atomic ratio 1: 2: 0.8～2, ball material mass ratio is 20～40: 1, after abrading-ball and raw material are put into ball grinder, ball grinder is vacuumized, after vacuumizing, charge into inert gas, drum's speed of rotation is 250～400rpm, the ball milling time is 70～120 hours, calcining is to remove remaining free carbon in air, and calcining heat is 430～550 ℃, obtains the composite catalyst powder.
2. the preparation method of a kind of nano silicon carbide molybdenum/aluminium sesquioxide compounding catalyst according to claim 1 is characterized in that: the atomic ratio of described molybdenum trioxide powder, aluminium powder and graphite powder is 1: 2: 1～1.5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100623003A CN1323756C (en) | 2005-12-28 | 2005-12-28 | Method for preparing nanometer molybdenum carbide/aluminium sesquioxide compounding catalyst |
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| CNB2005100623003A CN1323756C (en) | 2005-12-28 | 2005-12-28 | Method for preparing nanometer molybdenum carbide/aluminium sesquioxide compounding catalyst |
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| CN1323756C true CN1323756C (en) | 2007-07-04 |
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| CN113731455B (en) * | 2020-05-28 | 2023-10-10 | 中国石油化工股份有限公司 | Desulfurization catalyst with hydrogen production function, preparation method thereof and hydrocarbon oil desulfurization method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147478A (en) * | 1996-05-17 | 1997-04-16 | 浙江大学 | Normal-temp composition process of ultrafine tungsten carbide and titanium carbide powder |
| WO2002066371A2 (en) * | 2001-02-16 | 2002-08-29 | Battelle Memorial Institute | A catalyst and method of steam reforming |
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- 2005-12-28 CN CNB2005100623003A patent/CN1323756C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147478A (en) * | 1996-05-17 | 1997-04-16 | 浙江大学 | Normal-temp composition process of ultrafine tungsten carbide and titanium carbide powder |
| WO2002066371A2 (en) * | 2001-02-16 | 2002-08-29 | Battelle Memorial Institute | A catalyst and method of steam reforming |
Non-Patent Citations (1)
| Title |
|---|
| 催化新材料氮化钼和碳化钼的新进展 魏昭彬，张耀军，化学通报，第2期 1996 * |
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