CN1390638A - Carbon nanotube carried catalyst for synthesizing Rh-base methanol - Google Patents
Carbon nanotube carried catalyst for synthesizing Rh-base methanol Download PDFInfo
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- CN1390638A CN1390638A CN02125035A CN02125035A CN1390638A CN 1390638 A CN1390638 A CN 1390638A CN 02125035 A CN02125035 A CN 02125035A CN 02125035 A CN02125035 A CN 02125035A CN 1390638 A CN1390638 A CN 1390638A
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- carbon nanotube
- synthesizing
- catalyst
- base methanol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A carbon nanotube carried Rh-base catalyst for preparing methanol from synthetic gas is a Rh-MxOy atom family composed of Rh carried by multi-wall carbon nanotubes (MWNTs) and an oxide of the metal chosen from Ti, Zn, Mn, Ce, Cr, Ca and Mg. As the carbon nanotube has high hydrogen-bearing and the proteon and electron transferring performance, said catalyst has high activity (increased by 1.9 times) and selectivity (99%), high stability, less pollution, and wide temp range (220-290 deg.C).
Description
The present invention relates to a kind of catalyst of synthesising gas systeming carbinol, especially a kind of carbon nanotube loaded type rhodium base catalyst that is used for synthesizing methanol.
Existing synthesising gas systeming carbinol is at Cu-ZnO-Al
2O
3Catalyst is realized down, the improvement of catalyst afterwards mainly concentrates on the composition aspect of catalyst, for example: (US 4 for United States Patent (USP) in 1986,565,803) propose methanol synthesis catalyst and be made up of copper, zinc and a kind of dressing agent, dressing agent is made up of yttrium, lanthanum and actinium family element or their mixture; United States Patent (USP) in 1987 (US 4,666,945) proposes to replace aluminium oxide to be prepared into methanol synthesis catalyst with zirconia; 2000 Chinese patent (CN001274618) a kind of catalst for synthesis of methanol is proposed, this catalyst is made up of Cu-Zr-La (Ce)-Mn (Ti); 1998 Chinese patent (CN981173393) propose on the basis of copper, zinc, aluminium, to add IIIB family metal oxide and IVB family or VB, group vib metal oxide, form Cu-Zn-Al-M '-M " four component methanol synthesis catalysts.Also there are some patents on the preparation method, to do improvement, as: United States Patent (USP) in 2000 (US 6,114,279) proposes to prepare methanol synthesis catalyst with nano aluminium oxide and Nano zinc oxide film parcel nano cupric oxide; 1981 United States Patent (USP) (US 4,308,176) adopt the duct that zinc oxide is placed copper aluminum oxide spinelle, as catalst for synthesis of methanol; 1996 Chinese patent (CN961132663) disclose with ultrasonic wave radiation prepared by co-precipitation catalyst precursor, with the decentralization and the method for specific area of metal oxide in the raising catalyst.
The present invention aims to provide and is a kind ofly loaded on the CNT by highly active rhodium (Rh), metal oxide (MxOy) metallic atom, is used for synthesis gas (CO+H
2+ CO
2) system methyl alcohol catalyst.
The said catalyst of the present invention is rhodium and a kind of Ti of being selected from that loads on the multi-walled carbon nano-tubes (MWNTs), Zn, Zr, Mn, Ce, Cr, Ca, Rh-MxOy atom a small bundle of straw, etc. for silkworms to spin cocoons on that the metal oxide of Mg is formed is made carbon nanotube loaded oxide and is helped the rhodium base catalyst (Rh-MxOy/MWNTs) of urging, wherein Rh: M=1: (2～8) (mol ratio), Rh: MWNTs=1: (20～60) (weight ratio), Rh: M=1 particularly: 4～5 (mol ratios), Rh: MWNTs=1: 25～30 (weight ratios), MWNTs represents multi-walled carbon nano-tubes here.Said Rh can be from RhCl
3, Rh (Ac)
2Deng; Said MxOy represents metal oxide, and M is the metallic atom in the metal oxide, and subscript x and y represent the number of metallic atom and oxygen atom in the oxide molecule respectively, x=1～2, and y=1～3, these oxides can be by Zn (NO
3)
2, ZnCl
2, ZnCO
3Or TiCl
4, MnSO
4, Ce (NO
3)
3, Cr (NO
3)
3, Ca (NO
3)
2Or Mg (NO
3)
2Deng soluble-salt calcination or by these soluble-salts and alkali reaction in air, generate to decompose behind the hydroxide and obtain, participating in the alkali that reacts can be ammonium hydroxide and alkali metal hydroxide, alkali carbonate or bicarbonate, NaOH especially, Na
2CO
3, NaHCO
3
The used solvent of the present invention is selected water, alcohol or alcohol-water mixed liquid, and the alcohol here is meant methyl alcohol or ethanol.
Catalyst adopts the load of iso volumetric impregnation method.At first the corresponding solubility lead compound of Rh, the MxOy of metering is dissolved in H
2In O, alcohol or the alcohol-water mixed solution, use rotary evaporator to remove most of water behind dipping 10～30min, transfer to then in the constant temperature oven, 110～140 ℃ of oven dry, time 3～8h is then at 340～360 ℃, particularly 350～360 ℃ of calcining 3～4h also need pass through reduction before the use.
Advantage of the present invention is to utilize the storage hydrogen of CNT and transmit proton and the characteristic of electronics, makes that the catalytic activity of catalyst of the present invention is 1.9 times of similar catalyst (NC207) of present industrial use, and selectivity reaches 99%; Second advantage of the present invention is to make the production of catalyst and the pollution of dead catalyst recovery drop to minimum; The temperature range wide (220～290 ℃) of reduction that the 3rd advantage of the present invention is catalyst and use, the good stability of catalyst.
Further specify the present invention with embodiment below.
Example 1
With 0.263gRhCl
3And 3.73gZn (NO
3)
2Be dissolved in the appropriate amount of deionized water, adopt the iso volumetric impregnation method, rhodium, the zinc solution of above-mentioned preparation immersed in the CNT of 1.72g, make Rh/MWNTs=1: 20 (weight ratios), through 110 ℃ of oven dry 3h, in air, calcine 3h down again and obtain catalyst, this catalyst H in 350 ℃
2Down switching to synthesis gas behind the reduction 1h at 300 ℃, synthesis gas consist of CO: H
2: CO
2=1: 2: 0.2, flow velocity was 1600ml/h, under 523K, stablize 2h after, measuring its catalytic activity is 411mgMeOH/g
CatH, the methyl alcohol selectivity reaches 99%.
The evaluation method of example 2-6 Preparation of catalysts and catalytic activity is with example 1, the composition of catalyst and synthesis gas, and reaction temperature and pressure are as shown in the table.
| Embodiment | ? ? ????M xO y | Rh: M mol ratio | Rh: MWNTs weight ratio | Synthesis gas is formed CO: H 2∶CO 2 | Reaction temperature ℃ | Pressure MPa | Catalytic activity mgMeOH/ g cat·h | Selectivity % |
| ???2 | ????Cr 2O 3 | ????1∶5 | ????1∶25 | ????1∶2∶0.2 | ????250 | ????1 | ????385 | ????99 |
| ???3 | ????ZnO | ????1∶3 | ????1∶25 | ????1∶2∶0.2 | ????260 | ????1 | ????390 | ????99 |
| ???4 | ????ZnO | ????1∶4 | ????1∶33 | ????1∶2∶0.25 | ????240 | ????1 | ????375 | ????99 |
| ???5 | ????CaO | ????1∶4 | ????1∶20 | ????1∶2∶0.2 | ????250 | ????1 | ????274 | ????90 |
| ???6 | ????MgO | ????1∶6 | ????1∶25 | ????1∶2∶0.2 | ????245 | ????1 | ????295 | ????93 |
Example 7
Preparation Rh-ZrO
2/ CNTs catalyst, Preparation of catalysts method are with example 1, wherein Rh: Zr=1: 4 (mol ratios), and Rh: MWNTs=1: 20, use H
2Switch to synthesis gas behind the reducing catalyst 1h, synthesis gas consist of CO: H
2: CO
2=10: 2: 0.2, flow velocity was 1600ml/h, stablizes 2h at 563K, and measuring its catalytic activity is 177.6mgMeOH/g
CatH, selectivity is 99%.
Example 8
Method by example 1 prepares the Rh-CaO/MWNTs catalyst, different is Rh: Ca=1 wherein: 2 (mol ratios), and Rh: MWNTs=1: 35, calcining heat is 633K, uses H
2Switch to synthesis gas behind the reducing catalyst 1h, synthesis gas consist of CO: H
2: CO
2=10: 20: 2.5, flow velocity was 1600ml/h, stablizes 2h at 523K, and measuring its catalytic activity is 350mgMeOH/g
CatH, selectivity is 99%.
Example 9
Method by example 1 prepares Rh-Ce
2O
3/ MWNTs catalyst, wherein Rh: Ce=1: 5 (mol ratios), Rh: MWNTs=1: 30 (weight ratios), use H
2Reduction feeds synthesis gas behind the 1h, synthesis gas consist of CO: H
2: CO
2=1: 2: 0.2, flow velocity was 1600ml/h, was 395mgMeOH/g in the catalytic activity of 523K assaying reaction
CatH, selectivity is 99%.
Example 10
Prepare Rh-MnO by example 1 method
2/ MWNTs catalyst, wherein Rh: Mn=1: 2 (mol ratios), Rh: MWNTs=1: 40 (weight ratios), use H
2Reduction feeds synthesis gas behind the 1h, synthesis gas consist of CO: H
2: CO
2=1: 2: 0.2, flow velocity was 1600ml/h, was 330mgMeOH/g in the catalytic activity of 523 K assaying reactions
CatH, selectivity is 99%.
Example 11
Prepare Rh-ZnO/MWNTs catalyst, wherein Rh: Zn=1 by example 1 method: 8 (mol ratios), Rh: MWNTs=1: 60 (weight ratios), catalyst reduction and active testing condition are with example 1, and the catalytic activity measurement result is 300mgMeOH/g
CatH, selectivity is 99%.
Claims (7)
1, carbon nanotube loaded catalyst for synthesizing Rh-base methanol, it is characterized in that loading on rhodium and a kind of Ti of being selected from the multi-walled carbon nano-tubes MWNTs, Zn, Zr, Mn, Ce, Cr, Ca, Rh-MxOy atom a small bundle of straw, etc. for silkworms to spin cocoons on that the metal oxide of Mg is formed, Rh: M=1 in molar ratio wherein: (2～8), by weight Rh: MWNTs=1: (20～60).
2, carbon nanotube loaded catalyst for synthesizing Rh-base methanol as claimed in claim 1 is characterized in that said Rh in molar ratio: M=1: 4～5, and by weight Rh: MWNTs=1: 25～30.
3, carbon nanotube loaded catalyst for synthesizing Rh-base methanol as claimed in claim 1 is characterized in that said Rh is from RhCl
3, Rh (Ac)
2
4, carbon nanotube loaded catalyst for synthesizing Rh-base methanol as claimed in claim 1 is characterized in that the subscript x of said MxOy and y represent the number of metallic atom and oxygen atom in the oxide molecule, x=1～2, y=1～3 respectively.
5, carbon nanotube loaded catalyst for synthesizing Rh-base methanol as claimed in claim 1 is characterized in that said oxide is by Zn (NO
3)
2, ZnCl
2, ZnCO
3Or TiCl
4, MnSO
4, Ce (NO
3)
3, Cr (NO
3)
3, Ca (NO
3)
2, Mg (NO
3)
2Soluble-salt calcination or by these soluble-salts and alkali reaction in air generates to decompose behind the hydroxide and obtains.
6, carbon nanotube loaded catalyst for synthesizing Rh-base methanol as claimed in claim 5 is characterized in that said alkali is ammonium hydroxide and alkali metal hydroxide, alkali carbonate or bicarbonate.
7, carbon nanotube loaded catalyst for synthesizing Rh-base methanol as claimed in claim 6 is characterized in that said alkali metal hydroxide, and alkali carbonate or bicarbonate are NaOH, Na
2CO
3, NaHCO
3
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| CN02125035A CN1128665C (en) | 2002-07-02 | 2002-07-02 | Carbon nanotube carried catalyst for synthesizing Rh-base methanol |
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|---|---|---|---|
| CN02125035A CN1128665C (en) | 2002-07-02 | 2002-07-02 | Carbon nanotube carried catalyst for synthesizing Rh-base methanol |
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| CN1390638A true CN1390638A (en) | 2003-01-15 |
| CN1128665C CN1128665C (en) | 2003-11-26 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007093081A1 (en) | 2006-02-16 | 2007-08-23 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | Catalyst and process for syngas conversion |
| CN104056622A (en) * | 2013-03-20 | 2014-09-24 | 中国科学院大连化学物理研究所 | Rhodium/carbon nanotube catalyst and preparation method and application |
| CN107051552A (en) * | 2017-05-22 | 2017-08-18 | 安徽大学 | Preparation of magnetic carbon nanotube-loaded rhodium catalyst and application of catalyst in selective hydrogenation of nitrile rubber |
| CN109126818A (en) * | 2018-08-17 | 2019-01-04 | 新奥科技发展有限公司 | A kind of composite catalyst and preparation method thereof |
| CN115555028A (en) * | 2022-09-30 | 2023-01-03 | 四川蜀泰化工科技有限公司 | High-activity, high-selectivity and high-stability methanol synthesis catalyst and preparation method thereof |
-
2002
- 2002-07-02 CN CN02125035A patent/CN1128665C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007093081A1 (en) | 2006-02-16 | 2007-08-23 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | Catalyst and process for syngas conversion |
| CN101374761B (en) * | 2006-02-16 | 2011-04-27 | 中国科学院大连化学物理研究所 | Catalyst and conversion method for synthesis gas |
| CN104056622A (en) * | 2013-03-20 | 2014-09-24 | 中国科学院大连化学物理研究所 | Rhodium/carbon nanotube catalyst and preparation method and application |
| CN107051552A (en) * | 2017-05-22 | 2017-08-18 | 安徽大学 | Preparation of magnetic carbon nanotube-loaded rhodium catalyst and application of catalyst in selective hydrogenation of nitrile rubber |
| CN107051552B (en) * | 2017-05-22 | 2019-09-27 | 安徽大学 | Preparation of magnetic carbon nanotube-loaded rhodium catalyst and application of catalyst in selective hydrogenation of nitrile rubber |
| CN109126818A (en) * | 2018-08-17 | 2019-01-04 | 新奥科技发展有限公司 | A kind of composite catalyst and preparation method thereof |
| CN109126818B (en) * | 2018-08-17 | 2021-12-07 | 新奥科技发展有限公司 | Composite catalyst and preparation method thereof |
| CN115555028A (en) * | 2022-09-30 | 2023-01-03 | 四川蜀泰化工科技有限公司 | High-activity, high-selectivity and high-stability methanol synthesis catalyst and preparation method thereof |
| CN115555028B (en) * | 2022-09-30 | 2023-09-05 | 四川蜀泰化工科技有限公司 | Methanol synthesis catalyst and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1128665C (en) | 2003-11-26 |
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