CN1511636A - Catalyst for synthesizing two carbon containing oxide by co hydrogehation and preparing method - Google Patents

Catalyst for synthesizing two carbon containing oxide by co hydrogehation and preparing method Download PDF

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CN1511636A
CN1511636A CNA021608164A CN02160816A CN1511636A CN 1511636 A CN1511636 A CN 1511636A CN A021608164 A CNA021608164 A CN A021608164A CN 02160816 A CN02160816 A CN 02160816A CN 1511636 A CN1511636 A CN 1511636A
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catalyst
preparation
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component
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罗洪原
丁云杰
尹红梅
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The catalyst has the composition of Rh-Mn-Fe-M1-M2/SiO2, where Mn, Fe, M1 and M2 are co-catalyst, M1 is Li or Na, M2 is Ru or Ir. The Rh carrying amount is 0.1-3 %, the Mn/Rh weight ratio is 0.5-12, the Fe carrying amount is 0.01-0.5 %, the M1/Rh weight ratio is 0.01-1, and M2/Rh weight ratio is 0.1-1.0. The preparation process includes dissolving the components in solvent to obtain solution, soaking silica carrier and drying at 283-473K to prepare the catalyst. Before use, the catalyst is hydrogen reduced at 573-673K for at least one hr, or is dried and roasted at 473-673K for 2-20 hr. The present invention has low Rh carrying amount, high activity and high selectivity.

Description

The catalyst and the preparation method that are used for the synthetic c 2-oxygenates of CO hydrogenation
Technical field
The present invention relates to the catalyst of the synthetic c 2-oxygenates of a kind of CO of being used for hydrogenation, relate in particular to rhodium Quito component catalyst of c_2-oxygen compounds such as a kind of co hydrogenation synthesizing alcohol, acetate, acetaldehyde and ethyl acetate.
The invention still further relates to above-mentioned Preparation of catalysts method.
Background technology
In the face of world petroleum resource reduces day by day, price is more and more higher, and consumption is increasing, seeks the big problem that new energy sources has become the whole world to pay close attention to.Ethanol in the c_2-oxygen compound is antiknock gasoline and the gasoline additive that does not have pollution, and directly synthesizing alcohol especially is subject to people's attention.In recent years, the rhodium base catalyst that is promoted by various ingredients is subjected to extensive studies, has applied for patent quite a lot.For example, GB 1,501, and 891 is the Rh-Fe catalyst that supports, J6148437, and J62148438 adds the catalyst of Mg or Ir and Li for based on Rh, Mn.J59227831 is the Rh-Mn-Ir-Li catalyst that supports.J6032733 is for being that the catalyst of solvent and CN1179993 are the Rh-Mn-Fe catalyst that adds Li or Na with Rh, Mn, Fe, Li.The loading height that a common feature of foregoing invention catalyst is a rhodium, the space-time yield of synthetic c 2-oxygenates is not high enough on the unit metal rhodium, and the manufacturing expense of catalyst is too high to have limited them in industrial application.
Summary of the invention
The object of the present invention is to provide the catalyst of the synthetic c 2-oxygenates of a kind of CO of being used for hydrogenation.
Another object of the present invention is to provide above-mentioned Preparation of catalysts method.
In the catalyst provided by the invention, the loading of rhodium is low, but catalyst is overall active high, the catalyst that the catalysis efficiency of unit rhodium significantly improves.
For achieving the above object, catalyst provided by the invention, it mainly consists of: Rh-Mn-Fe-M 1-M 2/ SiO 2M 1Be alkali metal, as Li and Na; M 2Be metal Ru and Ir.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 carrying capacity of Fe is 0.01 to 0.5, and more suitably the Fe carrying capacity is 0.02 to 0.3, and only Fe carrying capacity is 0.04 to 0.2.M 1The weight ratio of/Rh is 0.01 to 1, 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, and better weight ratio is 0.2 to 0.8, and best weight ratio is 0.3 to 0.7.
According to the present invention, the Preparation of catalysts method is as follows:
Catalyst is by immersion process for preparing, and the most handy co-impregnation also can prepare with step impregnation method.Each component of catalyst can be the compound of chloride, nitrate or other solubilities, as the chloride of ammonia coordination, the complex compound of carbonyl coordination etc.Used solvent can be a water, also can be nonaqueous solvents, as methyl alcohol etc.
When using co-impregnation to prepare catalyst, the compound of each component of aequum is dissolved in the solvent, is mixed with certain density solution, be impregnated into then on the carrier silica gel.The amount of maceration extract will guarantee to flood all carriers at least.When using step impregnation method to prepare, the compound of each component is mixed with certain density maceration extract step impregnation respectively to silica, or the compound of at first selecting fractions is mixed with the solution of mixing, is impregnated on the silica earlier, and then floods the compound solution of all the other components.
The baking temperature of macerate can be 283K-473K, and the dry time can be 2 hours to 20 days, and the length of dry time is relevant with the height of baking temperature.When baking temperature was 373K to 393K, the dry time was 4 hours to 12 hours.Dried catalyst can be 473K to 673K roasting 2 hours to 20 hours, also can be directly as standby catalyst after drying.These standby catalyst before reaction in 573-723K with pure hydrogen or hydrogeneous gas reduction at least 1 hour.The catalyst that is made by the present invention has higher c_2-oxygen compound space-time yield.
The specific embodiment
With following embodiment the present invention is done detailed explanation.
Embodiment 1: Preparation of Catalyst 1
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, LiNO 3, Fe (NO 3) 2, H 2IrCl 6Aqueous solution impregnation of silica, after 383K dry 6 is little; Obtain 1%Rh-1%Mn-0.05%Fe-0.075%Li-0.5%Ir/SiO 2Catalyst.
Embodiment 2: Preparation of Catalyst 2
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, LiNO 3, Fe (NO 3) 2, H 2IrCl 6Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-1%Mn-0.1Fe-0.075%Li-0.5%Ir/SiO 2Catalyst.
Embodiment 3: Preparation of Catalyst 3
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, LiNO 3, Fe (NO 3) 2, H 2IrCl 6Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-1%Mn-0.05%Fe-0.1%Li-0.5%Ir/SiO 2Catalyst.
Embodiment 4: Preparation of Catalyst 4
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, NaNO 3, Fe (NO 3) 2, H 2IrCl 6Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-1%Mn-0.05%Fe-0.1%Na-0.5%Ir/SiO 2Catalyst.
Embodiment 5: Preparation of Catalyst 5
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, LiNO 3, Fe (NO 3) 2, RuCl 3Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-1%Mn-0.1%Fe-0.075%Li-0.5%Ru/SiO 2Catalyst.
Embodiment 6: Preparation of Catalyst 6
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, NaNO 3, Fe (NO 3) 2, RuCl 3Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-2%Mn-0.05%Fe-0.1%Na-0.5%Ru/SiO 2Catalyst.
Embodiment 7: Preparation of Catalyst 7
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, LiNO 3, Fe (NO 3) 2, H 2IrCl 6Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1.5%Rh-1.5%Mn-0.12%Fe-0.11%Li-0.5%Ir/SiO 2Catalyst.
Comparative example 1: comparative example Preparation of catalysts 1
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1.0%Rh/SiO 2Catalyst.
Comparative example 2: comparative example Preparation of catalysts 2
Containing aequum RhCl 3.xH 2The aqueous solution impregnation of silica of O after 383K dry 6 is little, obtains 1.0%Rh-1%Mn/SiO 2Catalyst.
Comparative example 3: comparative example Preparation of catalysts 3
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, LiNO 3, Fe (NO 3) 2, H 2IrCl 6Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-1%Mn-0.075%Li/SiO 2Catalyst.
Comparative example 4: comparative example Preparation of catalysts 4
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, Fe (NO 3) 2Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-1%Mn-0.05%Fe/SiO 2Catalyst.
Comparative example 5: comparative example Preparation of catalysts 5
Containing aequum RhCl 3.xH 2O, Mn (NO 3) 2, LiNO 3, H 2IrCl 6Aqueous solution impregnation of silica, after 383K dry 6 is little, obtain 1%Rh-1%Mn-0.075%Li-0.5%Ir/SiO 2Catalyst.
The synthesis gas reaction evaluation result of embodiment and comparative example catalyst is listed in the table 1.
By the result of table 1 as can be seen, catalyst Noble Metal Rhodium carrying capacity of the present invention is low, and the preparation method is simple, is used for c_2-oxygen compounds such as carbon monoxide synthesizing alcohol, acetate, acetaldehyde and has high activity and selectivity.The catalysis efficiency of synthetic c_2-oxygen compound is higher than previous catalyst significantly on the unit metal rhodium of catalyst, has bigger prospects for commercial application.
The catalyst performance of table 1 embodiment and comparative example
Reaction condition: raw material H 2/ CO=2 (volume ratio), reaction pressure: 3.0Mpa; Temperature: 583K; Volume space velocity: 13000h -1
Catalyst (weight %, all the other are SiO to the catalyst composition 2) Space-time yield gram/kilogram. hour Selectivity C%
Embodiment 1 ?1％Rh-1％Mn-0.075％Li-0.5％Ir- ?0.05％Fe ????460.2 ????62.3
Embodiment 2 ?1％Rh-1％Mn-0.075％Li-0.5％Ir- ?0.1％Fe ????453.1 ????60.4
Embodiment 3 ?1％Rh-1％Mn-0.1％Li-0.5％Ir- ?0.05％Fe ????445.7 ????60.1
Embodiment 4 ?1％Rh-1％Mn-0.1％Na-0.5％Ir- ?0.05％Fe ????438.3 ????60.4
Embodiment 5 ?1％Rh-1％Mn-0.075％Li-0.5％Ru- ?0.1％Fe ????428.6 ????58.3
Embodiment 6 ?1％Rh-2％Mn-0.1％Na-0.5％Ru- ?0.05％Fe ????432.7 ????57.4
Embodiment 7 ?1.5％Rh-1.5％Mn-0.075％Li- ?0.5％Ir-0.1％Fe ????509.1 ????64.3
Comparative example 1 ?1％Rh ????35.5 ????16.3
Comparative example 2 ?1％Rh-1％Mn ????270.3 ????34.9
Comparative example 3 ?1％Rh-1％Mn-0.075％Li ????331.6 ????56.8
Comparative example 4 ?1％Rh-1％Mn-0.05％Fe ????333.3 ????40.0
Comparative example 5 ?1％Rh-1％Mn-0.075％Li-0.5％Ir ????397.5 ????59.0

Claims (9)

1, the catalyst that is used for the synthetic c 2-oxygenates of CO hydrogenation, mainly the consisting of of catalyst: Rh-Mn-Fe-M 1-M 2/ SiO 2, Mn, Fe, M in the formula 1And M 2Be co-catalyst;
Wherein: M 1Be Li or Na; M 2Be Ru or Ir;
The carrying capacity of Rh is 0.1-3%, and the weight ratio of Mn/Rh is 0.5-12, and the weight ratio of Fe/Rh is 0.01～0.5, M 1The weight ratio of/Rh is 0.01～1, M 2The weight ratio of/Rh is 0.1～1.0.
2, a kind of method for preparing the described catalyst of claim 1 is dissolved in the compound of each component of aequum in the solvent, is mixed with solution, is impregnated on the silica supports, and drying is 2 hours～20 days under the 283K-473K temperature, makes preparing catalyst.
3, preparation method as claimed in claim 1 is characterized in that, described each component is the compound of chloride or nitrate solubility, and used solvent is water or nonaqueous solvents.
4, as claim 2 or 3 described preparation methods, it is characterized in that the chloride that described each component is the ammonia coordination or the complex compound of carbonyl coordination.
As claim 2 or 3 described preparation methods, it is characterized in that 5, described nonaqueous solvents is a methyl alcohol.
6, preparation method as claimed in claim 2 is characterized in that, described preparing catalyst before use, in 573-673K with pure hydrogen or hydrogeneous gas in-situ reducing at least 1 hour.
7, preparation method as claimed in claim 2 is characterized in that, the compound of described each component is impregnated on the silica supports, and dry back was in 473～673K roasting 2～20 hours.
As claim 2 or 7 described preparation methods, it is characterized in that 8, described dipping is co-impregnation or step impregnation method.
9, preparation method as claimed in claim 8 is characterized in that, the impregnation sequence of described step impregnation method is random order.
CNA021608164A 2002-12-30 2002-12-30 Catalyst for synthesizing two carbon containing oxide by co hydrogehation and preparing method Pending CN1511636A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102218329A (en) * 2010-04-15 2011-10-19 中国石油化工股份有限公司 Method for preparing C2 and oxygenated chemicals thereof by using synthesis gas
CN103521249A (en) * 2012-07-05 2014-01-22 中国科学院大连化学物理研究所 Phosphide catalyst for synthetic gas conversion and preparation method and application thereof
CN105363445A (en) * 2014-08-25 2016-03-02 中国科学院大连化学物理研究所 Method for preparing Rh-based catalyst, Rh-based catalyst and application

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102218329A (en) * 2010-04-15 2011-10-19 中国石油化工股份有限公司 Method for preparing C2 and oxygenated chemicals thereof by using synthesis gas
CN103521249A (en) * 2012-07-05 2014-01-22 中国科学院大连化学物理研究所 Phosphide catalyst for synthetic gas conversion and preparation method and application thereof
CN103521249B (en) * 2012-07-05 2016-08-24 中国科学院大连化学物理研究所 A kind of phosphide catalyst converted for synthesis gas and preparation method and applications
CN105363445A (en) * 2014-08-25 2016-03-02 中国科学院大连化学物理研究所 Method for preparing Rh-based catalyst, Rh-based catalyst and application
CN105363445B (en) * 2014-08-25 2018-04-06 中国科学院大连化学物理研究所 A kind of method for preparing Rh base catalyst and Rh bases catalyst and application

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