CN102850406A - Bridged complex formed by metal cobalt carbonyl cluster and La and Ce, and preparation method and application thereof - Google Patents
Bridged complex formed by metal cobalt carbonyl cluster and La and Ce, and preparation method and application thereof Download PDFInfo
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- CN102850406A CN102850406A CN2012103164733A CN201210316473A CN102850406A CN 102850406 A CN102850406 A CN 102850406A CN 2012103164733 A CN2012103164733 A CN 2012103164733A CN 201210316473 A CN201210316473 A CN 201210316473A CN 102850406 A CN102850406 A CN 102850406A
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- 0 C*(C)(C)N(CC1)C(*2)C2[C@]1[Rn](*)(O)O Chemical compound C*(C)(C)N(CC1)C(*2)C2[C@]1[Rn](*)(O)O 0.000 description 1
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Abstract
The invention discloses a bridged complex formed by a metal cobalt carbonyl cluster and La and Ce, a preparation method thereof and application of the complex in synthetic gas-to-oil (F-T reaction) fixed bed and slurry bed catalytic reactions. The complex has a general structural formula as described in the specification. The preparation method for a catalyst in the invention is simple and convenient; the elements of an auxiliary agent and active components are introduced in the form of molecules, the auxiliary agent and the active components are uniformly distributed, the effects of the auxiliary agent is more substantial, and activity and selectivity of the catalyst are effectively improved.
Description
The application is that number of patent application is 201010166936.3, and the applying date is 2010.05.10, and denomination of invention is divided an application for " a class cobalt bunch-different metal bridging title complex and as the preparation method and application of synthetic cyclostrophic oil catalyzer ".
Technical field
The present invention relates to the preparation method, constitutional features of a metalloid cobalt-carbonyl bunch and other different metal bridging title complex and as the preparation method and application of synthetic cyclostrophic oil (F-T building-up reactions) catalyzer.
Background technology
Cobalt-base catalyst is the catalyzer of a class excellent performance of the synthetic processing of Fischer-Tropsch (F-T) hydrocarbon product, has CO hydrogenation activity height, strong, the CO of F-T chainpropagation ability
2Selectivity low, the oxygenatedchemicals growing amount is few, stable and be difficult for the advantages such as carbon distribution and poisoning in the reaction process.For remedying the deficiency of single-activity metal, but in the preparation process of catalyzer, often need to introduce other index of modulation, such as carrier and auxiliary agent etc.Carrier commonly used has SiO
2, Al
2O
3, TiO
2, MgO, molecular sieve, diatomite and gac etc.Traditional auxiliary agent divides two large classes: metal oxide auxiliary agent (ZrO
2, TiO
2, ThO
2, CeO
2, La
2O
3Deng) and precious metal additive (Pt, Pd, Ru etc.).Lot of documents studies show that the interpolation of auxiliary agent can effectively improve activity, selectivity and the stability of catalyzer, but most of auxiliary agents all are the methods of flooding by respectively, finally the form with oxide compound is doped in the active ingredient, and the randomness that adjuvant component distributes is very strong, and clustering phenomena is also very serious.In order effectively to overcome the above problems, the present invention provide a kind of new auxiliary agent to introduce mode, thereby improve the auxiliary agent effect and have special practical value improving the auxiliary agent stochastic distribution.
Summary of the invention
The object of the invention is for adopting traditional dipping means that auxiliary agent is added in the active ingredient, adjuvant component distributes at random and inhomogeneous problem, provide a kind of bridging cobalt carbonyl different metal cluster title complex, the cobalt atom of cobalt bunch is zero oxidation state in such title complex, it is the active ingredient of FT catalysts, and rare earth or transition metal (Ti, Zr) exist with normal valence state, are the adjuvant components of FT catalysts.Prepare F-T synthetic oil cobalt-base catalyst take such title complex as presoma, thereby realize that at molecular level auxiliary agent mixes with the even of active ingredient, improve the activity and selectivity of catalyzer.
The different metal cluster title complex of cobalt carbonyl that contains the carboxyl bridge is divided into following nine classes by constitutional features:
1.Ln
2{ OOCR μ
3-CCo
3(CO)
9}
2{ OOCCF
3}
4{ (CO)
9Co
3μ
3-CRCOOH}
4(Ln=La, Ce, Eu) (I), typical structural formula is as follows:
Among the structural formula I, Ln represents rare earth element La and Ce, Eu; G represents cobalt Carbonyl Clusters fragment: (CO)
9Co
3μ
3-CR-(R=alkylidene group, benzyl or zero), its structural representation is as follows:
2.Ti
4(μ
3-O)
4(OCH
2CH
3)
4{μ-[(CO)
9Co
3(μ
3-CRCO
2)]}
4(II)；
Zr
2(μ-OCH(CH
3)
2)
2(OCH(CH
3)
2)
2{μ-[(CO)
9Co
3(μ
3-CRCO
2)]}
2{(CO)
9Co
3(μ
3-CRCO
2)}
2(III)。The typical structure formula is:
Among structural formula II, the III, the cobalt Carbonyl Clusters fragment of G representative as shown in structural formula I; Et representative-CH
2CH
3Pr representative-CH (CH
3)
2
3.Yb
4-O{μ-[(Co
3(CO)
9(μ
3-CRCOO)]}
6(IV)
The typical structure formula is:
Among the structural formula IV, the cobalt Carbonyl Clusters fragment of G representative as shown in structural formula I.
4.
Ln
2{OOCRμ
3-CCo
3(CO)
9}
2{OOCCF
3}
4{(CO)
9Co
3μ
3-CRCOOH}
4(THF)
2(Ln＝Yb，Sm)(V)；
Ln
2{OOCRμ
3-CCo
3(CO)
9}
2{OOCCF
3}
4{(CO)
9Co
3μ
3-CRCOOH}
2(THF)
2(Ln＝La，Ce)(VI)
Typical structural formula is shown below respectively:
Ln represents rare earth element Sm, Yb among the structural formula V; Ln represents rare earth element La and Ce among the structural formula VI, and THF represents tetrahydrofuran (THF) among structural formula V, the VI, the cobalt Carbonyl Clusters fragment of G representative as shown in structural formula I.
5.{[Co
3(CO)
9μ
3-CRCOOLn
3(μ-OOCCF
3)
6(THF)
3]
2Co(OH)
3}·2THF(Ln＝La，Ce，Sm，Eu)(VII)
The elementary cell that comprises two repetitions in this molecular structure, its basic cell structure formula is as follows:
Structural formula VII
(having ignored H atom and free THF molecule in the formula)
This molecular structure is to pass through CF by the elementary cell of structural formula VII representative
3COO-bridgingligand and OH-part and another elementary cell are formed by connecting has centrosymmetric cage structure, and metal Co is positioned at symmetry centre.In addition, also there are 2 free THF molecules in the molecular structure.Among the structural formula VII, Ln represents rare earth element La and Ce, Sm, Eu, and THF represents tetrahydrofuran (THF), and G represents cobalt Carbonyl Clusters fragment: (CO)
9Co
3CCR-(R=2H, alkylidene group, benzyl).
6.{La
12[Co
2(CO)
6μ-CC (COO)
2]
8(CF
3COO)
2016H
2O}4H
2Comprise the elementary cell of four repetitions in this molecular structure of O (VIII), its basic cell structure formula is as follows:
Structural formula VIII
(ignored free H in the formula
2The O molecule)
This molecular structure is to pass through CF by the elementary cell of structural formula VIII representative
3COO-bridgingligand and the cobalt Carbonyl Clusters part that contains carboxyl functional group respectively with the adjacent elementary cell ring texture that is formed by connecting.In addition, also there are 4 free H in the molecular structure
2The O molecule.Among the structural formula VIII, G represents cobalt Carbonyl Clusters fragment: (CO)
6Co
2CRCR-(R=2H, alkylidene group, benzyl).
7.{Ce
12[Co
2(CO)
6μ-CC(COO)
2]
8(CF
3COO)
24(CH
3COO)
4·8H
2O}·THF·17H
2O·CH
3COOCH
2CH
3(IX)
The elementary cell that comprises four repetitions in this molecular structure, its basic cell structure formula is as follows:
Structural formula IX
(ignored free THF molecule, CH in the formula
3COOCH
2CH
3Molecule and H
2The O molecule) this molecular structure is to pass through CF by the elementary cell of structural formula IX representative
3COO-bridgingligand and the cobalt Carbonyl Clusters part that contains carboxyl functional group respectively with the adjacent elementary cell ring texture that is formed by connecting.In addition, also there are 1 free THF molecule, 1 free CH in the molecular structure
3COOCH
2CH
3Molecule and 17 free H
2The O molecule.The cobalt Carbonyl Clusters fragment of G representative as shown in structural formula VIII among the structural formula IX.
Do catalyst precursor by described carboxyl bridging cobalt carbonyl cluster title complex, take organic solvent THF etc. as solvent, γ-Al
2O
3Or SiO
2Be carrier, prepare the cobalt-base catalyst that contains rare earth or titanium, zirconium auxiliary agent by dipping method.
The present invention also provides the application of described catalyzer in the reaction of F-T synthetic oil.
Advantage of the present invention:
1. has the title complex of clear and definite structure as catalyst precursor, for the distance of effectively controlling between auxiliary agent and active ingredient provides possibility, also for providing clue from the relation between Study of Catalyst structure and performance on the molecular level.
2. the mode take title complex as catalyst precursor is incorporated into auxiliary agent and active ingredient in the catalyzer simultaneously, has guaranteed the even distribution between auxiliary agent and active ingredient, for effective performance of auxiliary agent effect provides strong condition.
3. when the catalyzer of preparation was used for fixed-bed catalytic take such title complex as the presoma load, without roasting process, direct in-situ carried out the H before the catalyzed reaction
2The disadvantageous effects such as the migration of element in the roasting process, gathering and sintering have been avoided in reduction activation.
4. such title complex also can be used for starching the catalyzer of attitude bed F-T synthetic oil reaction.
Embodiment
Following examples will the present invention is further illustrated:
Embodiment 1
Ln
2{ OOC μ
3-CCo
3(CO)
9}
2{ μ-OOCCF
3}
4{ (CO)
9Co
3μ
3-CCOOH}
4(Ln=La, Ce, Eu) (I) synthetic
With (CO)
9Co
3CCOOH (0.500g, 1.0mmol) and Ln (OOCCF
3)
3(0.5mmol) be dissolved in the THF solvent, N in 50mL Schlenk bottle
2The lower reaction of protection, 30 ℃ of lower stirring 1h get atropurpureus solution, and vacuum desolventizes.Solid extracts with hot toluene, places after 2 days under the extracting solution room temperature and namely obtains 400mg left and right sides black coarse crystal, productive rate about 80% (in Ln).
Ultimate analysis (being calculated value in the %, bracket), C
74H
4Co
18F
12O
74Eu
2: C24.35 (24.22), H 0.43 (0.11), and Co 27.96 (28.91), and Eu 7.97 (8.28); IR (KBr, cm
-1) 2111 (m), 2054 (vs), 1708 (m), 1678 (m), 1608 (m), 1479 (w), 1466 (w), 1407 (w), 1368 (w), 1337 (w), 1265 (w), 1205 (m), 1155 (w), 1062 (w), 1028 (w), 781 (w), 723 (w), 528 (w), 504 (m).
C
74H
4Co
18F
12O
74La
2：C?24.80(24.40)，H?0.31(0.11)，Co?30.57(29.12)，La?6.26(7.63)；IR(KBr，cm
-1)2110(m)，2044(vs)，1670(m)，1620(m)，1540(m)，1385(s)，1339(m)，1205(m)，1149(w)，1085(w)，792(w)，753(w)，727(m)，554(m)，503(m)。
C
74H
4Co
18F
12O
74Ce
2：C?24.55(24.38)，H?0.48(0.11)，Co?28.57(29.10)，Ce?6.74(7.69)；IR(KBr，cm
-1)2109(m)，2044(vs)，1675(m)，1624(m)，1540(s)，1384(s)，1335(m)，1205(m)，1154(w)，1081(w)，792(w)，753(w)，723(m)，551(m)，504(m)。
Embodiment 2
Ti
4(μ
3-O)
4(OCH
2CH
3)
4μ-[(CO)
9Co
3(μ
3-CCO
2)]
4Synthesizing (II)
With (CO)
9Co
3CCOOH (0.9700g, 2.0mmol) and liquid Ti (OCH
2CH
3)
4(0.22mL, 1.0mmol) with THF as solvent, N in 50mL Schlenk bottle
2The lower reaction of protection is stirred 12h and is got atropurpureus solution under the room temperature, vacuum desolventizes.It is substantially colourless that the solid that obtains is washed till solution with ethanol, and the solid after then will cleaning is dissolved in the 20ml methylene dichloride, places 4 ℃ of lower placements a week, collects and obtain the 350mg crystal.Productive rate 70% (in Ti).
Ultimate analysis (being calculated value in the %, bracket), C
52H
20Co
12Ti
4O
52: C:26.18 (26.29), H:1.12 (0.85); IR (KBr, cm
-1) 2109 (m), 2054 (vs), 1633 (m), 1490 (w), 1382 (m), 1338 (w), 1120 (w), 1073 (w), 1030 (m), 927 (w), 727 (w), 618 (w), 553 (m), 535 (m), 502 (m).
Embodiment 3
Yb
4-O{ μ-[Co
3(CO)
9μ
3-CCOO] }
6Synthesizing (IV)
With (CO)
9Co
3CCOOH (0.500g 1.0mmol) and Yb (CF
3COO)
32H
2O (0.1263g 0.2467mmol) with THF as solvent, N in 50mL Schlenk bottle
2The lower reaction of protection, 30 ℃ of lower stirring 9h get atropurpureus solution, and vacuum desolventizes.Solid extracts with hot toluene, obtains black crystals after one week of placement under the extracting solution room temperature in dichloromethane solvent.
Ultimate analysis (being calculated value in the %, bracket): C
67Co
18O
69Yb
4, C:21.90 (21.85), O:30.08 (30.12), Co:28.90 (28.81), Yb:18.85 (18.79); IR (KBr, cm
-1): 2109 (m), 2011 (vs), 1708 (m), 1678 (m), 1619 (m), 1456 (w), 1386 (w), 1203 (m), 1152 (w), 1086 (w), 791 (w), 752 (w), 727 (w), 554 (w), 502 (m).
Embodiment 4
Ln
2{ OOC (CH
2)
2C
6H
4μ
3-CCo
3(CO)
9}
2{ OOCCF
3}
4{ (CO)
9Co
3μ
3-C C
6H
4(CH
2)
2COOH}
4(THF)
2(Ln=Yb, Sm) (V) synthetic
Take by weighing (CO)
9Co
3[μ
3-CC
6H
4(CH
2)
2COOH] (0.4039g, 0.6843mmol) and Yb (CF
3COO)
32H
2O (0.0936g, 0.1708mmol) or Sm (CF
3COO)
32H
2O (0.0632g, 0.1203mmol) with THF as solvent, N in 50mL Schlenk bottle
2Protect in lower 30 ℃ of water-baths and react.After reaction stops, removing reaction solvent under the vacuum.Toluene at Room Temperature extracts, and obtains puce solution, obtains the brown pressed powder under the low temperature.
Ultimate analysis (being calculated value in the %, bracket): molecular formula C
130H
68O
76Yb
2Co
18F
12, C:35.13 (34.89), H:1.12 (1.34), Co:24.24 (23.73), Yb:7.12 (7.74); IR (KBr, cm
-1): v (CO) 2101 (m), 2054 (vs), v (C=O) 1670 (vs), 1598 (s), v (C-F) 1205 (s), 1153 (m).
Ultimate analysis value (being calculated value in the %, bracket): molecular formula C
130H
68O
76Sm
2Co
18F
12, C:35.58 (35.18), H:1.23 (1.53), Co:24.50 (23.95), Sm:6.03 (6.78); IR (KBr, cm
-1): v (CO) 2103 (m), 2054 (vs), v (C=O) 1670 (s), 1623 (m), v (C-F) 1204 (s), 1153 (m).
Embodiment 5
Ln
2{ OOC (CH
2)
2C
6H
4μ
3-CCo
3(CO)
9}
2{ OOCCF
3}
4{ (CO)
9Co
3μ
3-CC
6H
4(CH
2)
2COOH}
2(THF)
2(Ln=La, Ce) (VI) synthetic
Take by weighing (CO)
9Co
3[μ
3-CC
6H
4(CH
2)
2COOH] (0.4057g, 0.6876mmol) and La (CF
3COO)
32H
2O (0.0882g, 0.1716mmol) or Ce (CF
3COO)
32H
2O (0.0889g, 0.1726mmol) with THF as solvent, N in 50mL Schlenk bottle
2Protect in lower 30 ℃ of water-baths and react.After reaction stops, removing reaction solvent under the vacuum.Obtain puce solution with methylbenzene extraction under the room temperature, the bottom has undissolved residue to occur.Filtrate obtains tan powder at low temperatures.
Ultimate analysis (being calculated value in the %, bracket): molecular formula C
92H
50O
54La
2Co
12F
12, C:34.63 (34.17), H:1.90 (1.60), Co:22.24 (21.87), La:7.75 (8.59); IR (KBr, cm
-1): (CO) 2102 (m), 2053 (vs), v (C=O) 1664 (s), 1598 (m), v (C-F) 1205 (s), 1151 (m).
Ultimate analysis value (being calculated value in the %, bracket): molecular formula C
92H
52O
54Ce
2Co
12F
12, C:34.52 (34.14), H:1.42 (1.60), Co:22.54 (21.87), Ce:9.12 (8.66); IR (KBr, cm
-1): v (CO) 2103 (m), 2502 (vs), v (C=O) 1664 (s), 1603 (m), v (C-F) 1204 (vs), 1147 (m).
Embodiment 6
{ [Co
3(CO)
9μ
3-CCCOOLn
3(μ-OOCCF
3)
6(THF)
3]
2Co (OH)
3(VII) synthetic of 2THF (Ln=La, Ce, Sm, Eu)
With (CO)
10Co
4HCCCOOH (0.500g, 1.0mmol) and Ln (OOCCF
3)
32H
2O (2mmol) with THF as solvent, N in 100mL Schlenk bottle
2Protect lower 30 ℃ of stirring reaction 5h to get purplish red solution, vacuum desolventizes.Solid extracts with hot toluene, and extracting solution refrigerates to get the garnet styloid.
C
80H
72Co
7F
36La
6O
60，IR(KBr，cm
-1)：2105(m)，2054(vs)，1687(vs)，1461(m)，1398(m)，1353(m)，1207(s)，1151(s)，1025(w)，927(w)，871(w)，723(w)。
C
80H
72Co
7F
36Ce
6O
60，IR(KBr，cm
-1)：2105(m)，2054(vs)，1687(vs)，1461(m)，1398(m)，1353(m)，1207(s)，1151(s)，1025(w)，927(w)，871(w)，723(w)。
Embodiment 7
{ La
12[Co
2(CO)
6μ-CC (COO)
2]
8(CF
3COO)
2016H
2O}4H
2O (VIII); { Ce
12[Co
2(CO)
6μ-CC (COO)
2]
8(CF
3COO)
24(CH
3COO)
48H
2O}THF17H
2OCH
3COOCH
2Synthesizing (IX)
Take by weighing (CO)
6Co
2CC (COOH)
2(0.100g, 0.250mmol) and Ln (OOCCF
3)
32H
2O (Ln=La, Ce) (0.3016mmol), with THF as solvent, 30 ℃ of stirring reactions 8 hours under the nitrogen protection in 30ml Schlenk bottle.After reaction stops, cooling, vacuum is removed solvent, with 30 ℃ of hot toluenes and the reacted product of ethyl acetate extraction, gets bright red filtrate.Filtrate adds the 2ml methylene dichloride, cultivates crystal under the room temperature nitrogen atmosphere.After a few days, obtain the sorrel crystal.
C
120H
40Co
16F
60La
12O
140，IR(KBr，cm
-1)：2103(m)，2065(vs)，2034(vs)，1672(vs)，1615(m)，1399(m)，1347(m)，1204(s)，1149(s)，1035(w)，846(w)，724(w)，517(w)。
The preparation of embodiment 8 catalyzer
γ-Al
2O
3Carrier anhydrates and surface hydroxyl to remove at 500 ℃ of lower roasting 10h first before use.Then under nitrogen protection, above various heteronuclear complex molecule presomas are dissolved in respectively in the organic solvent, use equi-volume impregnating, it is loaded to the γ-Al that anticipates
2O
3On the carrier.It is cobalt group catalyst synthesized that vacuum desolventizes the F-T that obtains containing auxiliary agent under the last room temperature.
The F-T building-up reactions performance evaluation of embodiment 9 catalyzer
The cobalt-base catalyst that contains various auxiliary agents of aforesaid method preparation is used for the F-T building-up reactions: experiment is carried out at fixed-bed reactor, and the catalyzed reaction procatalyst carries out first original position H
2Reduction.Reaction gas forms: CO/H
2/ Ar=10: 5: 1, air speed was 500/h, and reaction pressure is 2.0MPa, and temperature of reaction is 220 ℃.The gas-phase product on-line analysis, H in the tail gas
2, CO, CH
4And CO
2By the GC-8APT gas chromatograph analysis of the Shimadzu company that carbonaceous molecular sieve post TDX-01 is housed, adopt the TCD detector; C in the tail gas
2-C
4By the GC-8APF gas chromatograph analysis of the Shimadzu company that Propack-Q stationary phase chromatographic column is housed, adopt fid detector.Obtaining gas phase by above-mentioned two kinds of analytical resultss forms.Oil sample uses the Rtx-1 capillary column by the GC-2014 gas chromatographic analysis of Shimadzu company.
Reaction result shows that these catalyzer have preferably activity and selectivity to the CO hydrogenation reaction, and the catalyzer that especially contains Eu, Ce, Ti auxiliary agent has more excellent performance than independent cobalt-base catalyst.Compare with the catalyzer of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES load, the catalyzer carbon monoxide transformation efficiency that contains Eu, Ce, Ti auxiliary agent has improved respectively 1.1,1.8 and 1.5 times, C
5+Selectivity has all improved 1.2 times.Thereby this catalyzer for preparing in the molecular precursor mode obviously is better than the catalyzer of traditional way preparation.
Claims (5)
1. a metalloid cobalt-carbonyl bunch and the bridging title complex that La forms is characterized in that title complex has the general structure take following structural formula VIII as elementary cell:
Structural formula VIII
Among the structural formula VIII, G represents cobalt Carbonyl Clusters fragment: (CO)
6Co
2CRCR-(R=2H, alkylidene group, benzyl).
2. a metalloid cobalt-carbonyl bunch and the bridging title complex that Ce forms is characterized in that having the general structure take structural formula IX as elementary cell:
Structural formula IX
Among the structural formula IX, G represents cobalt Carbonyl Clusters fragment: (CO)
6Co
2CRCR-(R=2H, alkylidene group, benzyl).
3. the preparation method of the bridging title complex that forms of a metalloid cobalt-carbonyl claimed in claim 1 bunch and La is characterized in that: take by weighing (CO)
6Co
2CC (COOH)
2(0.100g, 0.250mmol) and La (OOCCF
3)
32H
2O (0.3016mmol), with THF as solvent, 30 ℃ of stirring reactions 8 hours under the nitrogen protection in the 30mlSchlenk bottle; After reaction stops, cooling, vacuum is removed solvent, with 30 ℃ of hot toluenes and the reacted product of ethyl acetate extraction, gets bright red filtrate; Filtrate adds the 2ml methylene dichloride, cultivates crystal under the room temperature nitrogen atmosphere; After a few days, obtain the sorrel crystal.
4. the preparation method of the bridging title complex that forms of a metalloid cobalt-carbonyl claimed in claim 2 bunch and Ce is characterized in that: take by weighing (CO)
6Co
2CC (COOH)
2(0.100g, 0.250mmol) and Ce (OOCCF
3)
32H
2O (0.3016mmol), with THF as solvent, 30 ℃ of stirring reactions 8 hours under the nitrogen protection in the 30mlSchlenk bottle; After reaction stops, cooling, vacuum is removed solvent, with 30 ℃ of hot toluenes and the reacted product of ethyl acetate extraction, gets bright red filtrate; Filtrate adds the 2ml methylene dichloride, cultivates crystal under the room temperature nitrogen atmosphere; After a few days, obtain the sorrel crystal.
5. the title complex of claim 1 or the carboxylic metal cobalt-carbonyl of 2 arbitrary described classes bunch and La or Ce bridging is directly as the F-T synthetic catalyst or as the presoma of F-T synthetic catalyst, and the application of this class catalyzer in F-T synthetic oil fixed bed and slurry attitude bed.
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| CN107573513A (en) * | 2017-08-28 | 2018-01-12 | 济南大学 | A kind of silver-bearing copper different metal cluster compound and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968136A (en) * | 1974-07-12 | 1976-07-06 | Union Carbide Corporation | Catalytic process for polyhydric alcohols and derivatives |
| JPS559047A (en) * | 1978-07-06 | 1980-01-22 | Agency Of Ind Science & Technol | Preparation of aldehyde |
| US4192777A (en) * | 1978-03-01 | 1980-03-11 | Exxon Research & Engineering Co. | Preparation and use of supported potassium (or rubidium)-Group VIII-metal cluster catalysts in CO/H2 Fischer-Tropsch synthesis reactions |
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2010
- 2010-05-10 CN CN201210316473.3A patent/CN102850406B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968136A (en) * | 1974-07-12 | 1976-07-06 | Union Carbide Corporation | Catalytic process for polyhydric alcohols and derivatives |
| US4192777A (en) * | 1978-03-01 | 1980-03-11 | Exxon Research & Engineering Co. | Preparation and use of supported potassium (or rubidium)-Group VIII-metal cluster catalysts in CO/H2 Fischer-Tropsch synthesis reactions |
| JPS559047A (en) * | 1978-07-06 | 1980-01-22 | Agency Of Ind Science & Technol | Preparation of aldehyde |
Non-Patent Citations (1)
| Title |
|---|
| 刘树堂: "Co_3(CO)_9(μ_3-PR)、Co_4(μ-CO)_2(CO)_8(μ_4-PR)_2和Co_2Fe(CO)_9(μ_3-PR)原子簇化合物合成与结构", 《高等学校化学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573513A (en) * | 2017-08-28 | 2018-01-12 | 济南大学 | A kind of silver-bearing copper different metal cluster compound and its preparation method and application |
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