阅读说明：本技术 一种用于合成气一步法直接合成醇醛类含氧产物的催化剂及应用 (Catalyst for directly synthesizing alcohol aldehyde oxygen-containing product by synthesis gas one-step method and application ) 是由 钟良枢 齐行振 林铁军 王新星 吕东 孙予罕 于 2020-04-09 设计创作，主要内容包括：本发明提供一种用于合成气一步法直接合成醇醛类含氧产物的催化剂及其应用。该催化剂包括复合氧化物和氢甲酰化固相催化剂；复合氧化物为CoM1复合氧化物或CoM1M2复合氧化物,M1选自Mg、Ca、Cu、Zn、Al、Zr、Mn、La和Ce中的一种或多种,M2选自Li、Na、K、Rb和Cs中的一种或多种。该催化剂体系经过还原及碳化得到用于合成气一步法直接合成醇醛类含氧产物的催化剂活性组分,该活性组分综合合成气制烯烃以及氢甲酰化催化剂的双重功能。催化剂制备相对简单,采用合适的发挥其双功能协同作用,用于合成气一步法直接合成醇醛类含氧产物反应体系中得到较高的醇醛类含氧产物选择性,同时催化剂稳定性也较好。(The invention provides a catalyst for directly synthesizing an aldol oxygen-containing product by a synthesis gas one-step method and application thereof, wherein the catalyst comprises a composite oxide and a hydroformylation solid-phase catalyst, the composite oxide is a CoM1 composite oxide or a CoM1M2 composite oxide, M1 is selected from one or more of Mg, Ca, Cu, Zn, Al, Zr, Mn, L a and Ce, and M2 is selected from one or more of L i, Na, K, Rb and Cs.)

1. A catalyst for directly synthesizing an aldol oxygen-containing product by a synthesis gas one-step method is characterized by comprising a composite oxide and a hydroformylation solid-phase catalyst in a mass ratio of 1: 5-5: 1, wherein the composite oxide is a CoM1 composite oxide or a CoM1M2 composite oxide, M1 is selected from one or more of Mg, Ca, Cu, Zn, Al, Zr, Mn, L a and Ce, and M2 is selected from one or more of L i, Na, K, Rb and Cs.

2. The catalyst of claim 1, wherein the molar ratio of Co to M1 is 1:10 to 10: 1.

3. The catalyst according to claim 1, wherein M2 is 0 to 5% by mass of the composite oxide.

4. The catalyst of claim 1, wherein the hydroformylation solid phase catalyst comprises an oxide of an active component selected from one or more of Rh, Pd, Ru and Co and a support selected from alumina, silica, zirconia, manganese oxide, activated carbon.

5. The catalyst of claim 4 wherein the active component is present in an amount of from 0.5% to 10% by weight of the support.

6. The catalyst according to claim 1, wherein the composite oxide is obtained by at least one preparation method selected from a coprecipitation method, a sol-gel method, a complexation method, and an impregnation method.

7. The catalyst of claim 1, wherein the hydroformylation solid phase catalyst is obtained by at least one preparation method selected from a coprecipitation method, a sol-gel method and an impregnation method.

8. The catalyst of any one of claims 1 to 7 is used for the direct synthesis of aldol oxygen-containing products by a synthesis gas one-step method.

9. Use according to claim 8, characterised in that it further comprises at least one of the following technical features:

1) when the catalyst is used for directly synthesizing alcohol aldehyde oxygen-containing products by a synthesis gas one-step method in a single reactor, a single-bed mixed catalyst state mode is adopted, and the composite oxide and the hydroformylation solid-phase catalyst are mixed in a physical mixing mode;

2) when the catalyst is used for directly synthesizing alcohol aldehyde oxygen-containing products by a synthesis gas one-step method in a single reactor, the composite oxide is filled at the upper part of a constant-temperature area of the reactor by adopting a double-bed catalyst state mode, and the hydroformylation solid-phase catalyst is filled at the lower part of the constant-temperature area of the reactor;

3) when the catalyst is used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method in the series-connected double reactors, the series-connected double reactors sequentially comprise a first reactor and a second reactor, the composite oxide is placed in a constant temperature area of the first reactor, and the hydroformylation solid-phase catalyst is placed in a constant temperature area of the second reactor.

10. Use according to claim 9, characterized in that it further comprises at least one of the following technical features:

11) in the characteristic 1), the composite oxide and the hydroformylation solid-phase catalyst are physically mixed, pressed into tablets and sieved to 40-60 meshes of particles;

12) in the characteristic 1), the composite oxide and the hydroformylation solid-phase catalyst are respectively tableted and sieved to 40-60 mesh particles and then are physically mixed;

13) in the characteristic 1), the reactor is a fixed bed reactor or a slurry bed reactor;

14) in the characteristic 1), before the catalyst is used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method, the catalyst is reduced and carbonized;

21) in the characteristic 2), the composite oxide tablets are screened to 40-60 mesh particles and then filled in the upper part of a constant temperature area of the reactor, and the hydroformylation solid-phase catalyst tablets are screened to 40-60 mesh particles and then filled in the lower part of the constant temperature area of the reactor;

22) in the characteristic 2), the reactor is a fixed bed reactor or a slurry bed reactor;

23) in the characteristic 2), before being used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method, the catalyst is reduced and carbonized;

31) in the characteristic 3), the composite oxide tablets are sieved to 40-60 meshes of particles and placed in a constant temperature area of the first reactor, and the hydroformylation solid-phase catalyst tablets are sieved to 40-60 meshes of particles and placed in a constant temperature area of the second reactor;

32) in the characteristic 3), the first reactor and the second reactor are fixed bed reactors or slurry bed reactors;

33) in the characteristic 3), before being used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method, the composite oxide is reduced and carbonized, and the hydroformylation solid-phase catalyst is reduced and carbonized.

Technical Field

The invention relates to the technical field of catalysts, in particular to a catalyst for directly synthesizing alcohol aldehyde oxygen-containing products by a synthesis gas one-step method and application thereof.

Background

The C1 chemical technology based on the catalytic conversion of the synthesis gas is one of the important ways to realize the clean and efficient conversion of coal and natural gas. Based on the catalytic conversion route of synthesis gas, the following reaction types are mainly used for realizing industrialization, namely Fischer-Tropsch synthesis, methanol-to-olefin, coal-to-glycol and the like. As an important route for catalytic conversion of synthesis gas, the synthesis gas to prepare mixed alcohol is always a key research field which is continuously concerned by the scientific community, but the industrialization of the synthesis gas is not realized until now. The mixed alcohol, especially the higher alcohol, has higher economic added value and practical application prospect, not only can be directly used as fuel for modern vehicles such as automobiles and the like, but also can be used as a gasoline additive or an intermediate product of fine chemicals, and can be widely applied to the fields of surfactants, plasticizers, detergents, cosmetics and the like.

In the reaction process of preparing mixed alcohol from synthetic gas, the reaction is carried out according to the mechanism and actual productIt is known that, in addition to a series of alcohols with different carbon numbers, a series of aldehydes, olefins, alkanes and CO with different carbon numbers are produced₂And the like, and how to convert the byproducts into the higher-value mixed alcohol as much as possible has important significance.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a catalyst for directly synthesizing an aldol oxygen-containing product from synthesis gas by a one-step method and an application thereof, wherein the catalyst comprises a composite oxide and a hydroformylation solid-phase catalyst in a mass ratio of 1: 5-5: 1, the composite oxide is a CoM1 composite oxide or a CoM1M2 composite oxide, M1 is selected from one or more of Mg, Ca, Cu, Zn, Al, Zr, Mn, L a and Ce, M2 is selected from one or more of L i, Na, K, Rb and Cs, the catalyst relates to the bifunctional synergy of the Co-based catalyst and the hydroformylation solid-phase catalyst, is used for preparing the aldol oxygen-containing product from the synthesis gas, and has higher selectivity of the aldol oxygen-containing product.

In order to achieve the above objects and other related objects, the invention provides a catalyst for directly synthesizing an aldol oxygen-containing product by a synthesis gas one-step method, which comprises a composite oxide and a hydroformylation solid-phase catalyst, wherein the mass ratio of the composite oxide to the hydroformylation solid-phase catalyst is 1: 5-5: 1, such as 1: 5-1: 1, 1: 1-2: 1 or 2: 1-5: 1, the composite oxide is a CoM1 composite oxide or a CoM1M2 composite oxide, M1 is selected from one or more of Mg, Ca, Cu, Zn, Al, Zr, Mn, L a and Ce, and M2 is selected from one or more of L i, Na, K, Rb and Cs.

Preferably, M1 is selected from one or more of Mn, Cu, Zn and Al.

Preferably, M2 is selected from one or more of Na and K.

Preferably, the mass ratio of the composite oxide to the hydroformylation solid-phase catalyst is 1: 2-2: 1.

Preferably, the molar ratio of Co to M1 is 1: 10-10: 1, such as 1: 10-1: 2, 1: 2-1: 1, 1: 1-2: 1, or 2: 1-10: 1. More preferably, the molar ratio of Co to M1 is 1:3 to 3: 1.

Preferably, M2 is present in an amount of 0% to 5%, such as 0% to 1% or 1% to 5% by weight of the composite oxide. More preferably, M2 is 1% to 2% by mass of the composite oxide.

Preferably, the hydroformylation solid phase catalyst comprises an oxide of an active component selected from one or more of Rh, Pd, Ru and Co and a support selected from alumina, silica, zirconia, manganese oxide, activated carbon. More preferably, the active component is selected from one or more of Rh and Ru and the support is selected from one or more of silica and activated carbon.

More preferably, the active component is 0.5% to 10%, such as 0.5% to 1% or 1% to 10% by weight of the carrier. Even more preferably, the active ingredient is 1% to 2% of the mass of the carrier.

Preferably, the composite oxide is obtained by at least one preparation method selected from a coprecipitation method, a sol-gel method, a complexation method and an impregnation method.

Preferably, the hydroformylation solid-phase catalyst is obtained by at least one preparation method of a coprecipitation method, a sol-gel method and an impregnation method.

The second aspect of the invention provides the use of the catalyst for the direct synthesis of the aldol oxygen-containing product from the synthesis gas by one-step method.

Preferably, one of the following technical features is also included:

1) when the catalyst is used for directly synthesizing alcohol aldehyde oxygen-containing products by a synthesis gas one-step method in a single reactor, a single-bed mixed catalyst state mode is adopted, and the composite oxide and the hydroformylation solid-phase catalyst are mixed in a physical mixing mode;

2) when the catalyst is used for directly synthesizing alcohol aldehyde oxygen-containing products by a synthesis gas one-step method in a single reactor, the composite oxide is filled at the upper part of a constant-temperature area of the reactor by adopting a double-bed catalyst state mode, and the hydroformylation solid-phase catalyst is filled at the lower part of the constant-temperature area of the reactor;

3) when the catalyst is used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method in the series-connected double reactors, the series-connected double reactors sequentially comprise a first reactor and a second reactor, the composite oxide is placed in a constant temperature area of the first reactor, and the hydroformylation solid-phase catalyst is placed in a constant temperature area of the second reactor.

More preferably, at least one of the following technical characteristics is also included:

11) in the characteristic 1), the composite oxide and the hydroformylation solid-phase catalyst are physically mixed, pressed into tablets and sieved to 40-60 meshes of particles;

12) in the characteristic 1), the composite oxide and the hydroformylation solid-phase catalyst are respectively tableted and sieved to 40-60 mesh particles and then are physically mixed;

13) in the characteristic 1), the reactor is a fixed bed reactor or a slurry bed reactor;

14) in the characteristic 1), before the catalyst is used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method, the catalyst is reduced and carbonized;

21) in the characteristic 2), the composite oxide tablets are screened to 40-60 mesh particles and then filled in the upper part of a constant temperature area of the reactor, and the hydroformylation solid-phase catalyst tablets are screened to 40-60 mesh particles and then filled in the lower part of the constant temperature area of the reactor;

22) in the characteristic 2), the reactor is a fixed bed reactor or a slurry bed reactor;

23) in the characteristic 2), before being used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method, the catalyst is reduced and carbonized;

31) in the characteristic 3), the composite oxide tablets are sieved to 40-60 meshes of particles and placed in a constant temperature area of the first reactor, and the hydroformylation solid-phase catalyst tablets are sieved to 40-60 meshes of particles and placed in a constant temperature area of the second reactor;

32) in the characteristic 3), the first reactor and the second reactor are fixed bed reactors or slurry bed reactors;

33) in the characteristic 3), before being used for directly synthesizing the aldol oxygen-containing product by the synthesis gas one-step method, the composite oxide is reduced and carbonized, and the hydroformylation solid-phase catalyst is reduced and carbonized.

Compared with the prior art, the invention has at least one of the following beneficial effects:

1) the invention provides a brand new catalyst design scheme, olefin is taken as an intermediate product, and the catalyst comprises a Co-based catalyst part and a hydroformylation catalyst part, so that the one-step synthesis of alcohol aldehyde oxygen-containing products by synthesis gas can be realized.

2) The catalyst has excellent comprehensive catalytic performance, the alcohol-aldehyde selectivity in the product distribution is high, the hydrocarbon selectivity is correspondingly reduced, and the product distribution is more economical.

3) The invention provides four catalyst filling modes and a plurality of reactor selection modes, which can be flexibly selected according to actual conditions and requirements, thereby achieving better comprehensive performance.

4) The catalyst has good stability, the reduction of the CO conversion rate within 80h can be controlled within 5 percent, meanwhile, the catalyst is relatively simple to prepare, and large-scale amplification preparation can be realized.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

The following examples were filled using one of the following methods:

1. catalyst A (i.e., the composite oxide) and catalyst B (i.e., the hydroformylation solid phase catalyst) were physically mixed, and then tableted and sieved to 40-60 mesh particles.

2. Catalyst A (i.e. composite oxide) and catalyst B (i.e. hydroformylation solid phase catalyst) are respectively tableted and sieved to 40-60 mesh particles, and then are physically mixed.

3. Catalyst A (namely composite oxide) and catalyst B (namely hydroformylation solid-phase catalyst) are respectively tableted and sieved to 40-60 meshes of particles, then A is filled at the upper part of a constant-temperature area of the reactor, and B is filled at the lower part of the constant-temperature area of the reactor.

4. Catalyst A (namely, composite oxide) and catalyst B (namely, hydroformylation solid-phase catalyst) are respectively tableted and sieved to 40-60 meshes of particles, then A is placed in a constant-temperature area of the first reactor, B is placed in a constant-temperature area of the second reactor, and the first reactor and the second reactor are connected in series.

[ example 1 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the catalysts A and B are physically mixed uniformly according to the mass ratio of 1:1, then tabletting and sieving are carried out to 40-60 meshes, then 1.5g of the catalyst and 3.0g of diluent quartz sand are weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 2 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 0.75g of catalyst and 3.0g of diluent quartz sand are respectively weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 3 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 0.75g of the catalyst is respectively weighed and physically mixed and diluted with 1.5g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 3. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO ═ 1.0) reaction was started with back pressure to reaction pressure, reaction temperature was further changed according to catalyst reactivity, and reaction was setThe conditions are that the reaction temperature is 240 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 4 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, two groups of catalysts are respectively tabletted and sieved to 40-60 meshes, then 0.75g of the catalyst is respectively weighed and physically mixed and diluted with 1.5g of diluent quartz sand, 4 is adopted to be filled into two sets of small-scale fixed bed reactors, the catalyst A-Co2Mn1Na1 is filled in the front set, and the catalyst B-Rh 1%/SiO are filled in the rear set₂. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the front set reaction temperature of 240 ℃ and the reaction space velocity of 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The reaction results are shown in Table 1, with a CO of 1.0 and a post-reaction temperature of 260 ℃.

[ example 5 ]

Catalyst A was prepared according to a Co/Mn/Zn molar ratio of 2:1:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Zn1Na 1%.

The active metal component of the catalyst B is Ru, which accounts for 1 percent of the mass of the carrier active carbon and is named as catalyst Ru1 percent/active carbon.

The catalysts A and B are in powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, and thenRespectively weighing 0.75g of catalyst, physically mixing and diluting with 1.5g of diluent quartz sand, and filling the mixture into a single set of small-scale fixed bed reactor by adopting 3. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 6 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in powder state, the two groups of catalysts are respectively tabletted and sieved to 40-60 meshes, then 10.0g of the catalysts are respectively weighed and physically mixed, 4 is adopted to be filled into two sets of slurry bed reactors, the catalyst A-Co2Mn1Na1 is filled in the front set, and the catalyst B-Rh 1%/SiO is filled in the rear set₂. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 15 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature of the front sleeve is 270 ℃, and the reaction air isSpeed 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The reaction temperature was 280 ℃ and the specific reaction results are shown in Table 1.

[ example 7 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 8 ]

The catalyst A is prepared according to the molar ratio of Co to Mn of 2:1, and the content of K accounts for 1 percent of the mass of the catalyst, and is named as catalyst Co2Mn1K1 percent.

The active metal component of the catalyst B is Rh which accounts for 1 percent of the mass of the carrier activated carbon and is named as catalyst Rh1 percent/activated carbon.

The catalysts A and B are both in powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and 2 is adopted to be filled into a single setIn a pilot plant fixed bed reactor. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 2.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂2.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature of 250 ℃ and the reaction space velocity of 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, where/CO is 2.0.

[ example 9 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 0.75g of the catalyst is respectively weighed and physically mixed and diluted with 1.5g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 3. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature of 230 ℃ and the reaction space velocity of 2000h^-1Reaction pressure 1.5MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 10 ]

The catalyst A is prepared according to the molar ratio of Co to Mn of 1:2, and the Na content accounts for 0.5 percent of the mass of the catalyst, and is named as the catalyst Co1Mn2Na0.5 percent.

The active metal component of the catalyst B is Ru and occupies SiO of a carrier₂1% by mass of the catalyst Ru 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 0.75g of the catalyst is respectively weighed and physically mixed and diluted with 1.5g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 3. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 15 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 0.5MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 11 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 1:1, with a Na content of 1% by mass of the catalyst, designated catalyst Co1Mn1Na 1%.

The active metal component of the catalyst B is Ru and occupies MnO as a carrier₂0.5% by mass of the catalyst Ru0.5%/MnO₂。

The catalysts A and B are both in a powder state, the catalysts A and B are physically mixed uniformly according to the mass ratio of 1:5, then tabletting and sieving are carried out to 40-60 meshes, then 1.5g of the catalyst and 3.0g of diluent quartz sand are weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 8000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is reduced to250 ℃ and switching to 10% syngas (H)₂/CO ═ 0.5) starting the carbonization process, and maintaining the carbonization space velocity at 2000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 3MPa, raw material gas H₂and/CO is 1.0. The catalyst can control the reduction of the CO conversion rate within 80h to be within 5 percent, has good stability, and the specific reaction result is shown in table 1.

[ example 12 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 1:1, with a Na content of 1% by mass of the catalyst, designated catalyst Co1Mn1Na 1%.

The active metal component of the catalyst B is Ru and occupies MnO as a carrier₂10% by mass of the catalyst Ru 10%/MnO₂。

The catalysts A and B are both in a powder state, the catalysts A and B are physically mixed uniformly according to the mass ratio of 5:1, then tabletting and sieving are carried out to 40-60 meshes, then 1.5g of the catalyst and 3.0g of diluent quartz sand are weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 8000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 5 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO ═ 0.5) starting the carbonization process, and maintaining the carbonization space velocity at 2000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 220 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 3MPa, raw material gas H₂and/CO is 1.0. The catalyst can control the reduction of the CO conversion rate within 80h to be within 5 percent, has good stability, and the specific reaction result is shown in table 1.

[ example 13 ]

The catalyst A is prepared according to the molar ratio of Co to Mg of 2:1, and the Na content accounts for 1 percent of the mass of the catalyst, and is named as catalyst Co2Mg1Na1 percent.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 14 ]

Catalyst A was prepared according to a Co/Ca molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Ca1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. The reduction process is finishedThen cooling to 250 ℃, and switching to 10% of synthesis gas (H)₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 15 ]

Catalyst A was prepared according to a Co/Cu/Al molar ratio of 2:1:1, with a Na content of 1% of the mass of the catalyst, designated catalyst Co2Cu1Al1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 16 ]

Catalyst A was prepared according to a Co/Cu/Zr molar ratio of 2:1:1, with a Na content of 1% by mass of the catalyst, designated catalyst Co2Cu1Zr1Na 1%.

The active metal component of the catalyst B is Rh and occupies SiO of the carrier₂1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 17 ]

Catalyst A was prepared according to a Co/L a molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co 2L a1Na 1%.

The active metal component of the catalyst B is Ru and occupies SiO of a carrier₂1% by mass of the catalyst Ru 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 18 ]

Catalyst A was prepared according to a Co/Ce molar ratio of 2:1, with Na content of 1% of the catalyst mass, named catalyst Co2Ce1Na 1%.

The active metal component of the catalyst B is Ru and occupies SiO of a carrier₂1% by mass of the catalyst Ru 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 1. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂1.0 of CO) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 19 ]

The catalyst A is prepared according to the Co/Mn molar ratio of 2:1, wherein the content of L i accounts for 1 percent of the mass of the catalyst, and is named as catalyst Co2Mn 1L i1 percent.

The active metal component of the catalyst B is Rh which accounts for 1 percent of the mass of the carrier activated carbon and is named as catalyst Rh1 percent/activated carbon.

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 2.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂2.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature of 250 ℃ and the reaction space velocity of 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, where/CO is 2.0.

[ example 20 ]

The catalyst A is prepared according to the molar ratio of Co to Mn of 2:1, and the Rb content accounts for 1 percent of the mass of the catalyst, and is named as a catalyst Co2Mn1Rb 1.

The active metal component of the catalyst B is Rh which accounts for 1 percent of the mass of the carrier activated carbon and is named as catalyst Rh1 percent/activated carbon.

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 2.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 2.0) back pressureStarting reaction at reaction pressure, further changing reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as follows, wherein the reaction temperature is 250 ℃, and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, where/CO is 2.0.

[ example 21 ]

The catalyst A is prepared according to the molar ratio of Co to Mn of 2:1, and the content of Cs accounts for 1 percent of the mass of the catalyst, and is named as catalyst Co2Mn1Cs1 percent.

The active metal component of the catalyst B is Rh which accounts for 1 percent of the mass of the carrier activated carbon and is named as catalyst Rh1 percent/activated carbon.

The catalysts A and B are both in powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 1.0g of the catalyst A and 0.5g of the catalyst B are weighed, and then the catalyst A and the catalyst B are physically mixed and diluted with 3.0g of diluent quartz sand, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 2.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂2.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature of 250 ℃ and the reaction space velocity of 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, where/CO is 2.0.

[ example 22 ]

The catalyst A is prepared according to the molar ratio of Co to Mn of 1:10, and the Na content accounts for 0 percent of the mass of the catalyst, and is named as catalyst Co1Mn10 percent.

The active metal component of the catalyst B is Rh and occupies carrier Al₂O₃1% by mass of the catalyst Rh 1%/SiO₂。

The catalysts A and B are both in powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes,then 0.75g of catalyst and 3.0g of diluent quartz sand are respectively weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 23 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 10:1, with a Na content of 5% by mass of the catalyst, designated catalyst Co10Mn1Na 5%.

The active metal component of the catalyst B is Rh and occupies MnO as a carrier₂1% by mass of the catalyst Rh 1%/MnO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 0.75g of catalyst and 3.0g of diluent quartz sand are respectively weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw materialsGas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 24 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Pd and occupies ZrO of the carrier₂1% by mass of the catalyst Pd 1%/ZrO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 0.75g of catalyst and 3.0g of diluent quartz sand are respectively weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

[ example 25 ]

Catalyst A was prepared according to a Co/Mn molar ratio of 2:1, with a Na content of 1% of the catalyst mass, designated catalyst Co2Mn1Na 1%.

The active metal component of the catalyst B is Co and occupies SiO of the carrier₂1% by mass of the catalyst Co 1%/SiO₂。

The catalysts A and B are both in a powder state, the two groups of catalysts are respectively tableted and sieved to 40-60 meshes, then 0.75g of catalyst and 3.0g of diluent quartz sand are respectively weighed and physically mixed and diluted, and the mixture is filled into a single set of small-scale fixed bed reactor by adopting 2. The reducing atmosphere was 10% H₂The reduction space velocity is 6000h^-1Reduction pressure 0.5MPa, the reduction temperature is 300 ℃, and the reduction time is 10 h. After the reduction process is finished, the temperature is reduced to 250 ℃, and 10 percent of synthesis gas (H) is switched to₂/CO 1.0) starting the carbonization process, and maintaining the carbonization space velocity at 6000h^-1Carbonizing at 250 deg.C under 0.5MPa for 24 hr, cooling to 200 deg.C, and introducing pure synthetic gas (H)₂/CO 1.0) back pressure to reaction pressure, further changing the reaction temperature according to the reaction performance of the catalyst, and setting the reaction conditions as the reaction temperature is 240 ℃ and the reaction space velocity is 2000h^-1Reaction pressure 1.0MPa, raw material gas H₂The specific reaction results are shown in table 1, with/CO ═ 1.0.

Table 1 example catalyst reaction results

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.