CN1724151A - A kind of catalyst that is used for the synthetic c_2-oxygen compound of CO hydrogenation - Google Patents
A kind of catalyst that is used for the synthetic c_2-oxygen compound of CO hydrogenation Download PDFInfo
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- CN1724151A CN1724151A CNA2004100546089A CN200410054608A CN1724151A CN 1724151 A CN1724151 A CN 1724151A CN A2004100546089 A CNA2004100546089 A CN A2004100546089A CN 200410054608 A CN200410054608 A CN 200410054608A CN 1724151 A CN1724151 A CN 1724151A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention provides a kind of Rh-Mn-Ti-M of consisting of
1-M
2/ SiO
2Catalyst, M
1Be alkali metal such as Li and Na; M
2Be a kind of of Ru, Fe and Ir or two kinds.According to the present invention, the carrying capacity of Rh is 0.1% to 3%, and the weight ratio of Mn/Rh is 0.5 to 12, and the weight ratio of Ti/Rh is 0.001 to 3, M
1The weight ratio of/Rh is 0.01 to 1.0, M
2The weight ratio of/Rh is 0.1 to 1.0.It is low that this catalyst has the Rh carrying capacity, and overall catalytic activity height, the advantage that the catalysis efficiency of the Rh of unit significantly improves.
Description
Technical field
The present invention relates to the catalyst of the synthetic c_2-oxygen compound of a kind of CO of being used for hydrogenation.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to above-mentioned Application of Catalyst.
Technical background
C_2-oxygen compound such as ethanol and acetaldehyde is an important chemical material, and particularly ethanol is subjected to paying close attention to widely as the value gasoline additive and the fuel that improve octane.The Rh of c_2-oxygen compounds such as the synthetic ethanol of selectivity is catalyst based, because it to generating unique selectivity of c_2-oxygen compound, is subject to people's attention extraordinarily.The catalyst based patent of Rh that priority has been applied for synthetic c_2-oxygen compound quite a lot in China and foreign countries.Its objective is by adding the method for various auxiliary agents, improve catalyst based activity and the selectivity that synthetic c_2-oxygen compound of Rh.For example GB1501891 is for being the loaded Rh-Fe catalyst of auxiliary agent with Fe.US4096164 is loaded Rh-Mo catalyst.J59227831 has invented a kind of usefulness Mn, Ir, three kinds of improved Rh of auxiliary agent of Li are catalyst based, uses 5%Rh-1.17%Ir-0.11%Mn-0.021%Li/SiO
2Catalyst is with CO/H
2=9 gaseous mixture is made unstripped gas, at 10.0Mpa, and 280-300 ℃ of reaction down, obtaining with acetate is main synthetic product.The selectivity of acetate reaches 67.1%, and space-time yield reaches 347 grams per liters hour.J6032733 is the catalyst with Rh, Mn, Li, Fe solvent.The common feature of these catalyst is loading height of Rh, generally at 4-5%, or is higher than 5%.Because Rh is a noble metal, too high Rh loading has limited the commercial Application of these catalyst.In CN1177521A, once applied for a kind of Rh-Ti-Mn-M of consisting of
1-M
2/ SiO
2Catalyst, M
1Be Ru, Fe, Ir or Ni, M
2Be K, Li or Mg.The Rh carrying capacity of this catalyst is 1%, and the catalysis efficiency of Rh is enhanced than previous catalyst, but from industrialization demands, further improved necessity is arranged still, with consumption that reduces Rh to greatest extent and the expense that reduces catalyst.
Summary of the invention
The objective of the invention is to provide a kind of multicomponent and low Rh loading and have greater activity and catalyst and on this catalyst, carry out the process of the synthetic c_2-oxygen compound of CO hydrogenation optionally.
It is low that catalyst provided by the invention has the Rh carrying capacity, and overall catalytic activity height, the advantage that the catalysis efficiency of unit rhodium significantly improves.
This catalyst consist of Rh-Mn-Ti-M
1-M
2/ SiO
2, M
1Be alkali metal such as Li and Na; M
2Be a kind of of Ru, Fe and Ir or two kinds.According to the present invention, the carrying capacity of Rh is 0.1% to 3%, and more suitably carrying capacity is 0.3% to 2%, and only carrying capacity is 0.7% to 1.5%.The weight ratio of Mn/Rh is 0.5 to 12, and more suitably weight ratio is 0.5 to 10, and only weight ratio is 1 to 8.The weight ratio of Ti/Rh is 0.001 to 3, and more suitably weight ratio is 0.001 to 2, and only weight ratio is 0.001 to 0.5.M
1The weight ratio of/Rh is 0.01 to 1.0, more suitably is 0.02 to 0.5, and only weight ratio is 0.04 to 0.2.M
2The weight ratio of/Rh is 0.1 to 1.0, more suitably is 0.1 to 0.9, and only weight ratio is 0.2 to 0.8.
According to the present invention, the Preparation of catalysts method is as follows:
Catalyst is by step impregnation method or co-impregnation preparation.Rh in the catalyst, Mn, M
1And M
2Component can be the compound of chloride, nitrate or other solubility.The compound of Ti component can be an organic titanate, as tetraethyl titanate, and butyl titanate, the chloride of titanium such as TiCl
4Or other soluble compound.Used solvent can be a water, also can be nonaqueous solvents, as methyl alcohol, ethanol etc.
When using co-impregnation to prepare catalyst, the compound of the various components of aequum is dissolved in the solvent, is made into certain density solution, be impregnated on the catalyst then.The amount of maceration extract will guarantee to flood all carriers at least.The baking temperature of macerate can be room temperature to 200 ℃, and the dry time can be 2 hours to 20 days.The length of drying time is relevant with the height of baking temperature.When baking temperature was 100 ℃ to 120 ℃, be 4 hours to 50 hours drying time, is preferably 4 hours to 30 hours.Dried catalyst can be 200 ℃ to 400 ℃ roastings 1 to 20 hour, also can be directly as preparing catalyst after drying.
When using step impregnation method, a kind of compound of or some kinds of components is made into certain density maceration extract together, is impregnated into earlier on the silica, drying or again after the roasting is flooded the compound of other component again.The drying of macerate is relevant with the program of step impregnation with roasting condition.The baking temperature of macerate can be room temperature to 200 ℃, and the dry time is 2 hours to 20 days.The length of drying time is relevant with the height of baking temperature.When baking temperature was 100 ℃ to 120 ℃, be 4 hours to 50 hours drying time, is preferably 4 hours to 30 hours.Dried catalyst can be 200 ℃ to 700 ℃ roastings 1 to 20 hour.Sintering temperature and time change with the program of dipping and the addition of each component of catalyst.After all components dipping and drying are finished directly as preparing catalyst, or after calcination process again as preparing catalyst.
These preparing catalysts place the pure H of reactor before reaction
2Or contain H
2Gas in-situ reducing at least 1 hour.But when needing, standby catalyst is used pure H in the reduction reactor outside online before the reactor of packing into
2Or contain H
2Gas in-situ reducing at least 1 hour under normal pressure or pressurized conditions, the catalyst after the reduction in reduction reactor after Passivation Treatment, draw off preserve standby.Said Passivation Treatment refers to, and reduction finishes that temperature of reactor reduced to room temperature or during near room temperature, with inert gas such as N
2, Ar or CO
2Blow down remaining H in the reactor
2, in inert gas, add micro-O then
2Or air, make the catalyst activity surface adsorb O lentamente
2, and be in the operating process that the catalyst under the high activity state burns and damages because of unexpected ingress of air after avoiding reducing.
The catalyst that the present invention makes has higher activity, higher c_2-oxygen compound space-time yield in the course of reaction that is used for the synthetic c_2-oxygen compound of CO hydrogenation.
The specific embodiment
The present invention is further illustrated with the following example.
Embodiment 1: with finite concentration Ti (OC
2H
5)
4Ethanolic solution dipping 20-40 purpose silica-gel carrier is treated etoh solvent volatilization back in 110 ℃ of dryings 5 hours, in 700 ℃ of roastings 4 hours, makes and contains the TiO that Ti is 0.0025wt.%
2/ SiO
2Use certain density RhCl
3, Mn (NO
3)
2, LiNO
3And H
2IrCl
6The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1%Rh-2%Mn-0.0025%Ti-0.075%Li-0.5%Ir/SiO 110 ℃ of dryings 20 hours
2Catalyst.
Embodiment 2: with finite concentration Ti (OC
2H
5)
4Ethanolic solution dipping 20-40 purpose silica-gel carrier treats that etoh solvent volatilization back in 110 ℃ of dryings 5 hours, in 600 ℃ of roastings 4 hours, makes the TiO of titaniferous 0.005%
2/ SiO
2All the other and embodiment 1 obtain standby 1%Rh-2%Mn-0.005%Ti-0.075%Li-0.5%Ir/SiO together
2Catalyst.
Embodiment 3: with the identical method of embodiment 1, make earlier and contain the TiO that Ti is 0.0025wt%
2/ SiO
2, use certain density RhCl then
3, Mn (NO
3)
2, LiNO
3And Fe (NO
3)
2The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1%Rh-2%Mn-0.0025%Ti-0.075%Li-0.05%Fe/SiO 110 ℃ of dryings 20 hours
2Catalyst.
Embodiment 4: make earlier with embodiment 1 identical method and contain the TiO that Ti is 0.0025wt%
2/ SiO
2, use certain density RhCl then
3, Mn (NO
3)
2, LiNO
3And RuCl
3The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1%Rh-2%Mn-0.0025%Ti-0.075%Li-0.3%Ru/SiO 110 ℃ of dryings 20 hours
2Catalyst.
Embodiment 5: make earlier with embodiment 2 identical methods and contain the TiO that Ti is 0.0025wt%
2/ SiO
2, use certain density RhCl then
3, Mn (NO
3)
2, LiNO
3, H
2IrCl
6And Fe (NO
3)
2The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1%Rh-2%Mn-0.005%Ti-0.1%Li-0.5%Ir-0.05%Fe/SiO 110 ℃ of dryings 20 hours
2Catalyst.
Embodiment 6: with finite concentration Ti (OC
2H
5)
4Ethanolic solution dipping 20-40 purpose silica-gel carrier is treated etoh solvent volatilization back in 110 ℃ of dryings 5 hours, in 500 ℃ of roastings 4 hours, makes and contains the TiO that Ti is 0.01wt%
2/ SiO
2, use certain density RhCl then
3, Mn (NO
3)
2, NaNO
3And H
2IrCl
6The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1%Rh-1%Mn-0.01%Ti-0.1%Na-0.5%Ir/SiO 110 ℃ of dryings 20 hours
2Catalyst.
Embodiment 7: make earlier with embodiment 2 identical methods and contain the TiO that Ti is 0.0025wt%
2/ SiO
2, use certain density RhCl then
3, Mn (NO
3)
2, LiNO
3And H
2IrCl
6The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1.3%Rh-2%Mn-0.005%Ti-0.075%Li-0.5%Ir/SiO 110 ℃ of dryings 20 hours
2Catalyst.
Comparative example 1: use certain density RhCl
3, Mn (NO
3)
2, LiNO
3And H
2IrCl
6The SiO that aqueous solution dipping is above-mentioned
2,, obtain standby 1%Rh-2%Mn-0.075%Li-0.5%Ir/SiO 110 ℃ of dryings 6 hours
2Catalyst.
Comparative example 2: make earlier with embodiment 1 identical method and to contain the TiO that Ti is 0.0025wt%
2/ SiO
2, use certain density RhCl then
3, LiNO
3And H
2IrCl
6The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1%Rh-0.0025%Ti-0.075%Li-0.5%Ir/SiO2 catalyst 110 ℃ of dryings 20 hours.
Comparative example 3: make earlier with embodiment 1 identical method and to contain the TiO that Ti is 0.0025wt%
2/ SiO
2, use certain density RhCl then
3, Mn (NO
3)
2And LiNO
3The TiO that aqueous solution dipping is above-mentioned
2/ SiO
2,, obtain standby 1%Rh-2%Mn-0.0025%Ti-0.075%Li/SiO 110 ℃ of dryings 20 hours
2Catalyst.
Embodiment and comparative example catalyst are at 320 ℃, 3.0MPa, 12500h
-1And H
2The unstripped gas of/CO volume ratio=2 carries out CO hydrogenation reaction evaluation result and lists in the table 1.
Find out from the reaction result of table 1, the Rh carrying capacity of catalyst of the present invention is low, the catalysis efficiency that the active selectivity height of c_2-oxygen compound such as synthesizing alcohol and acetaldehyde, the metal Rh of unit of catalyst are gone up synthetic c_2-oxygen compound is higher than previous catalyst significantly and has better prospects for commercial application.
The CO hydrogenation reaction result of table 1 embodiment
| Embodiment | Catalyst is formed wt% | Space-time yield gram/kilogram. hour | Selectivity C% |
| 1 | 1Rh-2Mn-0.0025Ti-0.075Li-0.5Ir | 453.4 | 57.2 |
| 2 | 1Rh-2Mn-0.005Ti-0.075Li-0.5Ir | 449.3 | 56.4 |
| 3 | 1Rh-2Mn-0.0025Ti-0.075Li-0.05Fe | 438.7 | 54.9 |
| 4 | 1Rh-2Mn-0.0025Ti-0.075Li-0.3Ru | 442.6 | 54.4 |
| 5 | 1Rh-2Mn-0.005Ti-0.1Li-0.5Ir-0.05Fe | 468.2 | 58.2 |
| 6 | 1Rh-1Mn-0.01Ti-0.1Na-0.5Ir | 451.3 | 56.8 |
| 7 | 1.3Rh-2Mn-0.005Ti-0.075Li-0.5Ir | 487.8 | 59.3 |
| Comparative example | |||
| 1 | 1Rh-2Mn-0.075Li-0.5Ir | 340.0 | 55.4 |
| 2 | 1Rh-0.0025Ti-0.075Li-0.5Ir | 158.4 | 46.1 |
| 3 | 1Rh-2Mn-0.0025Ti-0.075Li | 317.2 | 53.3 |
Claims (13)
1, a kind of catalyst that is used for the synthetic c_2-oxygen compound of CO hydrogenation, its expression formula is:
Rh-Mn-Ti-M
1-M
2/ SiO
2, in the formula:
M
1Be Li or Na; M
2Be that Ir, Ru are or/and Fe; The Rh carrying capacity is 0.1-3%; The weight ratio of Mn/Rh is 0.5-12; The weight ratio of Ti/Rh is 0.001-3; M
1The weight ratio of/Rh is 0.01-1.0; M
2The weight ratio of/Rh is 0.1-1.0.
2, the catalyst of claim 1 is characterized in that, wherein: the Rh carrying capacity is 0.7-1.5%; The weight ratio of Mn/Rh is 1-8; The weight ratio of Ti/Rh is 0.001-0.5; M
1The weight ratio of/Rh is 0.04-0.2; M
2The weight ratio of/Rh is 0.2-0.8.
3, a kind of method for preparing the described catalyst of claim 1, its key step is:
Compound titanium solution is impregnated on the silica-gel carrier, and the macerate drying is or/and Rh is flooded in roasting more respectively, and Mn, Li or Na, Ir, Ru be or/and the Fe compound solution, and macerate is room temperature to 200 ℃ drying 2 hours to 20 days, catalyst.
4, the preparation method of claim 3 is characterized in that, floods Rh respectively, Mn, and Li or Na, Ir, Ru are or/and the order of Fe compound solution is arbitrarily.
5. the preparation method of claim 3 is characterized in that, compound titanium solution is impregnated on the silica-gel carrier, and the macerate drying is or/and Rh and Mn are flooded in roasting again, Li or Na, and Ir, Ru are or/and Fe compound solution formulated together; Macerate is normal temperature to 200 ℃ drying 2 hours to 20 days, catalyst.
6. claim 3 or 5 preparation method is characterized in that when described baking temperature was 100 to 120 ℃, be 4 hours to 30 hours drying time.
7. claim 3 or 5 preparation method is characterized in that the catalyst that obtains was 150 ℃ to 700 ℃ roastings 1 to 20 hour.
8, claim 3 or 5 preparation method is characterized in that titanium compound is Ti (OC
2H
5)
4, Ti (OC
4H
9)
4, TiCl
4Or the compound of other solubility; The compound of Rh, Mn, Ru, Ir and Fe is the compound of chloride, nitrate or other solubility.
9, claim 3 or 5 preparation method is characterized in that the used solvent of described solution is water, methyl alcohol or ethanol.
10, claim 3 or 5 preparation method is characterized in that the catalyst that makes places the pure H of reduction reactor before use
2Or contain H
2Gas in-situ reducing at least 1 hour under normal pressure or pressurized conditions.
11, claim 3 or 5 preparation method is characterized in that, the catalyst that obtains is used pure H in the reduction reactor outside online before the reactor of packing into
2Or contain H
2Gas in-situ reducing at least 1 hour under normal pressure or pressurized conditions, the catalyst after the reduction in reduction reactor after Passivation Treatment, draw off preserve standby.
12, the preparation method of claim 11 is characterized in that, described Passivation Treatment refers to, and reduction finishes that temperature of reactor reduced to room temperature or during near room temperature, uses inert gas N
2, Ar or CO
2Blow down remaining H in the reactor
2, in inert gas, add O then
2Or air, make the catalyst activity surface adsorb O lentamente
2, and be in the operating process that the catalyst under the high activity state burns and damages because of unexpected ingress of air after avoiding reducing.
13, the application of the catalyst of claim 1 in the synthetic c_2-oxygen compound reaction of CO hydrogenation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100546089A CN1724151A (en) | 2004-07-22 | 2004-07-22 | A kind of catalyst that is used for the synthetic c_2-oxygen compound of CO hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2004100546089A CN1724151A (en) | 2004-07-22 | 2004-07-22 | A kind of catalyst that is used for the synthetic c_2-oxygen compound of CO hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1724151A true CN1724151A (en) | 2006-01-25 |
Family
ID=35923861
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|---|---|---|---|
| CNA2004100546089A Pending CN1724151A (en) | 2004-07-22 | 2004-07-22 | A kind of catalyst that is used for the synthetic c_2-oxygen compound of CO hydrogenation |
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