CN104772150A - Cobalt-based catalyst for synthesis gas one-step preparation of mixed alcohol and aldehyde, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a cobalt-based catalyst for one-step synthesis of mixed alcohols and aldehydes and its preparation method and application. The catalyst includes: Co, Mn, Cu, alkali metals and additives; the preparation method includes: 1) According to the composition ratio of the catalyst, the nitrate of Cu, Co, Mn and additives is prepared into a mixed salt solution; 2) according to the composition ratio of the catalyst, the precipitant containing alkali metal is prepared into a precipitant solution; 3) the The mixed salt solution of step 1) and the precipitant solution of step 2) flow co-precipitate; 4) After the precipitation is completed, aging, after separation, washing, drying and roasting, the catalyst is obtained; or after the precipitation is completed, aging and separation , washing, drying and roasting, impregnated with alkali metal solution, dried and roasted to obtain the catalyst. The catalyst obtained in the invention has the advantages of high selectivity for mixed alcohols and aldehydes, low cost, easy preparation, easy industrial scale-up and the like.

Description

Cobalt-based catalyst for one-step synthesis of mixed alcohols and aldehydes, its preparation method and application

technical field

The invention relates to a catalyst, its preparation method and application, in particular to a cobalt-based catalyst used for the one-step synthesis of mixed alcohols and aldehydes, as well as its preparation method and application.

Background technique

The research on the synthesis of mixed alcohols with coal and natural gas as the main raw materials is one of the important contents of C ₁ chemistry. The application prospect of mixed alcohol has become increasingly clear. As a fuel additive, it has good solubility, volatility, driving operability and high octane number. In addition, it can also be used as a raw material and clean fuel for some chemical products.

At present, there have been reports on the synthesis of mixed alcohols directly from synthesis gas. The most representative catalysts of this type are the following four:

(1) Modified methanol synthesis catalyst (Cu/ZnO/A1 ₂ O ₃ , ZnO/Cr ₂ O ₃ ): typical patents include EP0034338A2 and US4513100. This type of catalyst was first developed by Italian Snam Company and German Lugi Company.

(2) Modified F-T synthetic Cu-Co catalyst: The French Institute of Petroleum (IFP) first developed a Cu-Co co-precipitated low-carbon alcohol catalyst, with patents US4122110, 4291126 and GB2118061, 2158730.

(3) Anti-sulfur MoS ₂ catalyst: a molybdenum-based sulfide catalyst developed by DOW Corporation of the United States (patent US4882360).

(4) Noble metal Rh-based catalysts (such as US4014913 and 4096164): After adding one or two transition metal or metal oxide promoters to the supported Rh catalyst, it has higher activity and selectivity for the synthesis of low-carbon alcohols, especially The selectivity to C ₂ ⁺ alcohols is high, and the product is mainly ethanol.

All of the above catalyst systems can obtain a certain amount of oxygen-containing products, and the oxygen-containing products basically exist in the form of mixed alcohols, but there are few reports on the research on the oxygen-containing products containing a large amount of aldehydes at the same time. Aldehydes have a wide application value in fine chemical industry. The traditional method of preparing aldehydes is hydroformylation reaction, that is, the direct reaction of olefins and synthesis gas to prepare aldehydes. However, due to the expensive raw material olefins, the economy is limited to a certain extent.

Contents of the invention

The technical problem to be solved by the present invention is to provide a cobalt-based catalyst for the one-step synthesis of mixed alcohols and aldehydes, as well as its preparation method and application. The catalyst can be used to prepare mixed alcohols and aldehydes by one-step synthesis gas with lower price, which has economic advantages and industrial application value.

In order to solve the above-mentioned technical problems, the cobalt-based catalyst used for syngas one-step preparation of mixed alcohols and aldehydes of the present invention includes: cobalt (Co), manganese (Mn), copper (Cu), alkali metals and additives;

Wherein, the molar ratio of Mn/Co is 0～10 (that is, the molar ratio x of Mn/Co is 0≤x≤10, preferably 0.5≤x≤2); the content of alkali metal is based on the mass of alkali metal oxide in the catalyst For percentage calculation, the range y is 0<y≤10%, preferably 0.5%<y≤2%;

The molar ratio of Cu/Co ranges from 0 to 10, preferably 0.1 to 1;

The additive is selected from at least one of transition metals, rare earth metals or alkaline earth metals, and the molar ratio of the additive to Co is in the range of 0-10, preferably 0.1-1.

The alkali metal is selected from lithium (Li), sodium (Na), potassium (K) or cesium (Cs), preferably sodium.

The transition metals include: Fe, Ni, Zr, Zn, Ru, Rh or Pd, etc.;

The rare earth metals include: La or Ce, etc.;

Alkaline earth metals include: Mg, Ca or Ba, etc.;

In addition, the present invention also discloses a preparation method of the above-mentioned catalyst, comprising the following steps:

(1) According to the composition ratio of the catalyst, the nitrate of Cu, Co, Mn and additives is formulated into a mixed salt solution (i.e. a uniform mixed solution with a certain concentration);

(2) according to the composition ratio of catalyst, the precipitating agent containing alkali metal is formulated into precipitating agent solution (i.e. a uniform solution of certain concentration);

Wherein, the precipitation agent is selected from at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate or potassium hydroxide;

(3) At 10-100°C and pH 6-12, co-precipitate the mixed salt solution of step (1) and the precipitant solution of step (2), that is, simultaneously combine the mixed salt solution of step (1) and the precipitant solution of step (2) (2) the precipitant solution is added dropwise in the precipitator;

(4) After the precipitation is over, age at 10-100°C for 0.5-24h; after the aging, follow the steps (5A) or (5B) below to obtain the catalyst:

(5A) After aging, after separation, washing, drying and roasting, the catalyst is obtained;

(5B) After aging, separation, washing, drying and roasting are performed to obtain a catalyst precursor, which is impregnated with the alkali metal solution, dried and roasted to obtain a catalyst.

In the step (1), the molar concentration of the total metal in the mixed salt solution ranges from 0.01 to 10 mol/L.

In the step (2), the precipitating agent is preferably sodium carbonate; the molar concentration of the precipitating agent solution ranges from 0.01 to 10 mol/L.

In the step (3), the mixing volume ratio of the mixed salt solution and the precipitant solution is 1:5 to 5:1, preferably 1:2 to 2:1; and preferably at 50 to 80°C and pH 7 to 9, Co-precipitate the mixed salt solution in step (1) and the precipitant solution in step (2) in parallel.

In the step (4), it is preferably aged at 50-80° C. for 1-5 hours.

In the step (5A) or (5B), the drying temperature is 50-150°C, preferably 100-120°C; the drying time is 1-24h, preferably 10-12h; the calcination temperature is 200-800°C, preferably 300-400°C °C; the roasting time is 0.5-24h, preferably 2-5h.

In the step (5B), the concentration range of the alkali metal solution is 0.1mol/L-4.0mol/L, preferably 0.5mol/L-1.0mol/L; the immersion temperature is generally room temperature, and the immersion time can be 1-24h; Preferably, the precursor of the catalyst is impregnated with the alkali metal solution in equal volume (ie, according to the water absorption ratio of 1:1).

Furthermore, the invention discloses the application of the catalyst, that is, it is used in the catalytic reaction of syngas one-step preparation of mixed alcohol and aldehyde.

Among them, the catalytic reaction conditions are: the reaction temperature is 150-350°C, preferably 200-300°C; the working pressure is 0.1-13Mpa, preferably 2-6Mpa, especially preferably 6Mpa; the reaction space velocity is 100-10000h ^-1 , preferably 2000- 6000h ^-1 , especially preferably 6000h ^-1 ; the synthesis gas is composed of H ₂ and CO, and the molar ratio of H ₂ /CO is 0.1-10, preferably 1-3.

The catalyst needs to be activated before it is used in the catalytic reaction of syngas to produce mixed alcohols and aldehydes in one-step method, wherein the activation conditions are: in a dilute hydrogen atmosphere, the temperature is gradually raised to 150-600°C, preferably 200-400°C; 1~24h, preferably 6~12h.

The diluted hydrogen atmosphere is a mixture of hydrogen and inert gas, preferably a mixture of hydrogen and nitrogen, wherein the molar ratio of hydrogen is 10% to 50%, preferably 10%; the space velocity of the diluted hydrogen atmosphere is 1000 to 20000h ^-1 , preferably 20000h ^-1 .

In the present invention, mixed alcohols include methanol, ethanol, and normal and isomeric alcohols with more than 2 carbon atoms, and the highest carbon number can be more than 20; mixed aldehydes include acetaldehyde and normal and isomeric alcohols with more than 3 carbon atoms. Aldehyde, the carbon number can be up to 10 or more.

The catalyst obtained in the present invention has the advantages of high selectivity of mixed alcohols and aldehydes, low cost, easy preparation and easy industrial scale-up, etc., wherein the selectivity of the total oxygen-containing compounds can reach more than 50C%, and the oxygen-containing compounds _above C The proportion in the oxygen compound can be as high as 90 wt%, and by changing the proportion of active components in the catalyst, the mass ratio of mixed alcohols and mixed aldehydes in the oxygen compound can be adjusted between 0.5 and 2.

Detailed ways

In the following examples, the synthesis gas involved is composed of CO and H ₂ .

Example 1

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.2/1/1 (molar ratio) A mixed solution with a total metal concentration of 2 mol/L was formed in a certain amount of deionized water. Dissolve Na ₂ CO ₃ in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2 mol/L.

Using the double-drop co-precipitation method, 224mL of the above mixed solution and 136mL of the precipitant solution were co-precipitated, wherein the mother solution was deionized water (100ml), the pH of the titration environment was controlled to be 8, and the titration temperature was controlled at 65 ° C. The titration was complete Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes from synthesis gas. The reaction device is a fixed-bed reactor. The atmosphere is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h ^-1 , the reduction temperature (gradient temperature can be increased) is 250°C, and the time is 5h.

After the reduction process is finished, lower the target reaction temperature (ie 220° C.), back pressure the reactor to 6.0 MPa with 10% (molar ratio) synthesis gas, and vent it after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 2

Dissolve Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) in a certain amount of deionized water according to Co/Mn=1/1 (molar ratio) to form a total metal concentration of 2mol/L mixed solution. Dissolve Na ₂ CO ₃ in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2 mol/L.

Using the double-drop co-precipitation method, 210mL of the above mixed solution and 215mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother liquor, the pH of the titration environment was controlled to be 8, and the titration temperature was controlled at 65 ° C. The titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven with programmed temperature rise to 120°C and dried for 12 hours, after grinding evenly, it was heated to 330°C with programmed temperature and roasted for 3 hours to obtain the precursor of the catalyst .

Using an equal-volume impregnation method, the precursor of the catalyst is impregnated with _Na2CO3 aqueous solution, and the content of Na is 1% (based on the mass of _Na2O relative to the mass of the catalyst precursor), wherein _the impregnation temperature is room temperature, and the impregnation time is Then, put it in a fume hood overnight, put it in an oven at 60°C and dry it overnight (that is, dry it for 12 hours). To get a catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h ^-1 , the reduction temperature (gradient temperature can be increased) is 250°C, and the time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 240°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 3

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=1.5/1/1 (molar ratio) A mixed solution with a total metal concentration of 2 mol/L was formed in a certain amount of deionized water. Dissolve Na ₂ CO ₃ in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2 mol/L.

Using the double-drop co-precipitation method, 187mL of the above mixed solution and 204mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother liquor, the pH of the titration environment was controlled to be 8, the titration temperature was controlled at 65°C, and the titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, after being centrifuged and washed for 6 times, it was placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 330°C for 3 hours to obtain the catalyst precursor body.

Using an equal-volume impregnation method, the precursor of the catalyst is impregnated with _Na2CO3 aqueous solution, and the content of Na is 1% (based on the mass of _Na2O relative to the mass of the catalyst precursor), wherein _the impregnation temperature is room temperature, and the impregnation time is for 20 hours, then put it in a fume hood overnight, and put it in an oven at 60°C for overnight drying (that is, drying for 12 hours). After grinding evenly, heat it up to 330°C for 3 hours, press it into tablets and crush it to 40-60 mesh. , get a catalyst.

The catalyst is used in the mixed alcohol and aldehyde reaction of syngas production. The reaction device is a fixed bed reactor. The atmosphere is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h ^-1 , the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 230°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 4

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.2/1/1 (molar ratio) Form a mixed solution with a total metal concentration _of 2mol/L in a certain amount of deionized water, and dissolve _Na2CO3 in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2mol/L.

Using the double-drop co-precipitation method, 323mL of the above mixed solution and 125mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother liquor, the pH of the titration environment was controlled to be 8, and the titration temperature was controlled at 65°C. The titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, after being centrifuged and washed for 6 times, it was placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 330°C for 3 hours to obtain the catalyst precursor body.

Using an equal-volume impregnation method, impregnate the precursor of the catalyst with _Na2CO3 aqueous solution, the content of Na is 3% (based on the mass of _Na2O relative to the mass of the catalyst precursor), wherein the impregnation temperature is room temperature, and the impregnation time is 10h , and then placed in a fume hood overnight, placed in an oven at 60°C for overnight drying (that is, drying for 12 hours), after grinding evenly, it was roasted at 330°C for 3 hours, pressed into tablets and crushed to 40-60 meshes to obtain catalyst.

The catalyst is used in the mixed alcohol and aldehyde reaction of syngas production. The reaction device is a fixed bed reactor. The atmosphere is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h ^-1 , the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 230°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 5

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.2/1/1 (molar ratio) Form a mixed solution with a total metal concentration _of 2mol/L in a certain amount of deionized water, and dissolve _Na2CO3 in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2mol/L.

Using the double-drop co-precipitation method, 254mL of the above mixed solution and 183mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother liquor, the pH of the titration environment was controlled to be 8, and the titration temperature was controlled at 65 ° C. The titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours, ground evenly and then roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h-1, the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 12000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 6

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.1/1/1 (molar ratio) Form a mixed solution with a total metal concentration _of 2mol/L in a certain amount of deionized water, and dissolve _Na2CO3 in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2mol/L.

Using the double-drop co-precipitation method, 218mL of the above mixed solution and 163mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother liquor, the pH of the titration environment was controlled to be 8, and the titration temperature was controlled at 65 ° C. The titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 8000h ^-1 , the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 7

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.6/1/1 (molar ratio) Form a mixed solution with a total metal concentration _of 2mol/L in a certain amount of deionized water, and dissolve _Na2CO3 in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2mol/L.

Using the double-drop co-precipitation method, 217mL of the above mixed solution and 135mL of the precipitant solution were co-precipitated, wherein the mother liquor was deionized water (100ml), the pH of the titration environment was controlled to be 8, the titration temperature was controlled at 65°C, and the titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 8000h ^-1 , the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 8

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.2/1/2 (molar ratio) Form a mixed solution with a total metal concentration _of 2mol/L in a certain amount of deionized water, and dissolve _Na2CO3 in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2mol/L.

Using the double-drop co-precipitation method, 176mL of the above mixed solution and 221mL of the precipitant solution were co-precipitated, wherein the mother solution was deionized water (100ml), the pH of the titration environment was controlled to be 8, the titration temperature was controlled at 65°C, and the titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 8000h ^-1 , the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 9

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=1.2/1/2 (molar ratio) Form a mixed solution with a total metal concentration _of 2mol/L in a certain amount of deionized water, and dissolve _Na2CO3 in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2mol/L.

Using the double-drop co-precipitation method, 169mL of the above mixed solution and 201mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother liquor, the pH of the titration environment was controlled to be 8, the titration temperature was controlled at 65°C, and the titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours, ground evenly and then roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 8000h ^-1 , the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 10

Combine Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O, Mn(NO ₃ ) ₂ (50%) and Zr(NO ₃ ) ₄ ·5H ₂ O by Cu/Co/Mn /Zr=0.2/1/1/0.15 (molar ratio) is dissolved in a certain amount of deionized water to form a mixed solution with a total metal concentration of 1mol/L. Dissolve K ₂ CO ₃ in a certain amount of deionized water to form a precipitant solution with a K ⁺ concentration of 1 mol/L.

Using the double-drop co-precipitation method, 243mL of the above mixed solution and 231mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother solution, the pH of the titration environment was controlled to be 9, and the titration temperature was controlled at 80 ° C. The titration was complete. Finally, it was aged in the mother liquor at 80°C for 12 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 400°C for 5 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 10000h ^-1 , the reduction temperature is 300°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 6000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 1.8, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 11

Combine Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O, Mn(NO ₃ ) ₂ (50%) and Ce(NO ₃ ) ₃ ·6H ₂ O by Cu/Co/Mn /Ce=0.2/1/1/0.1 (molar ratio) is dissolved in a certain amount of deionized water to form a mixed solution with a total metal concentration of 2mol/L. Dissolve Na ₂ CO ₃ in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2 mol/L.

Using the double-drop co-precipitation method, 167mL of the above mixed solution and 224mL of the precipitant solution were co-precipitated, wherein the mother liquor was deionized water (50ml), the pH of the titration environment was controlled to be 7, the titration temperature was controlled at 65°C, and the titration was complete. Finally, it was aged in the mother liquor at 80°C for 24 hours. After centrifugation and washing for 6 times, it was placed in an oven and dried at 100°C for 12 hours. After grinding evenly, it was roasted at 400°C for 8 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 3000h ^-1 , the reduction temperature is 350°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 240°C, the reaction space velocity is 5000h ^-1 , the working pressure is 4.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 1.8, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 12

Mix Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O, Mn(NO ₃ ) ₂ (50%) and Mg(NO ₃ ) ₂ ·6H ₂ O by Cu/Co/Mn /Mg=0.4/1/1.2/0.05 (molar ratio) is dissolved in a certain amount of deionized water to form a mixed solution with a total metal concentration of 0.5mol/L, and Na ₂ CO ₃ is dissolved in a certain amount of deionized water to form Na ⁺ Precipitant solution with a concentration of 0.5mol/L.

Using the double-drop co-precipitation method, 356mL of the above mixed solution and 412mL of the precipitant solution were co-precipitated, wherein the mother liquor was deionized water (150ml), the pH of the titration environment was controlled to be 8, the titration temperature was controlled at 65°C, and the titration was complete. Finally, it was aged in the mother liquor at 65°C for 4 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 24 hours. After grinding evenly, it was roasted at 350°C for 12 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 15000h ^-1 , the reduction temperature is 300°C, and the reduction time is 5h.

After the reduction process is finished, lower the target reaction temperature, back pressure the reactor to 6.0 MPa with 10% syngas (molar ratio), and vent it after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 5000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2.0, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 13

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.2/1/1 (molar ratio) Form a mixed solution with a total metal concentration _of 2mol/L in a certain amount of deionized water, and dissolve _Na2CO3 in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2mol/L.

Using the double-drop co-precipitation method, 254mL of the above mixed solution and 183mL of the precipitant solution were co-precipitated. Among them, deionized water (100ml) was selected as the mother liquor, the pH of the titration environment was controlled to be 8, and the titration temperature was controlled at 65 ° C. The titration was complete. Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours, ground evenly and then roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h-1, the reduction temperature is 250°C, and the reduction time is 5h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 240°C, the reaction space velocity is 12000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 14

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.2/1/1 (molar ratio) A mixed solution with a total metal concentration of 2 mol/L was formed in a certain amount of deionized water. Dissolve Na ₂ CO ₃ in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2 mol/L.

Using the double-drop co-precipitation method, 224mL of the above mixed solution and 136mL of the precipitant solution were co-precipitated, wherein the mother solution was deionized water (100ml), the pH of the titration environment was controlled to be 8, and the titration temperature was controlled at 65 ° C. The titration was complete Finally, it was aged in the mother liquor at 65°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 12 hours. After grinding evenly, it was roasted at 400°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes from synthesis gas. The reaction device is a fixed-bed reactor. The atmosphere is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h ^-1 , the reduction temperature (gradient temperature can be increased) is 300°C, and the time is 5h.

After the reduction process is finished, lower the target reaction temperature (ie 220° C.), back pressure the reactor to 6.0 MPa with 10% (molar ratio) synthesis gas, and vent it after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 6000h ^-1 , the working pressure is 8.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Example 15

Dissolve Cu(NO ₃ ) ₂ ·3H ₂ O, Co(NO ₃ ) ₂ ·6H ₂ O and Mn(NO ₃ ) ₂ (50%) according to Cu/Co/Mn=0.6/1/1 (molar ratio) A mixed solution with a total metal concentration of 2 mol/L was formed in a certain amount of deionized water. Dissolve Na ₂ CO ₃ in a certain amount of deionized water to form a precipitant solution with a Na ⁺ concentration of 2 mol/L.

Using the double-drop co-precipitation method, 217mL of the above mixed solution and 135mL of the precipitant solution were co-precipitated, wherein the mother solution was deionized water (100ml), the pH of the titration environment was controlled to be 9, the titration temperature was controlled at 65 ° C, and the titration was complete. Finally, it was aged in the mother liquor at 80°C for 2 hours, centrifuged and washed 6 times, then placed in an oven and dried at 120°C for 24 hours. After grinding evenly, it was roasted at 330°C for 3 hours to obtain the catalyst.

The catalyst is used in the reaction of mixed alcohols and aldehydes produced from synthesis gas. The reaction device is a fixed-bed reactor. It is a mixed gas of H ₂ and N ₂ , H ₂ /mixed gas=10% (molar ratio), the reduction space velocity is 20000h ^-1 , the reduction temperature is 250°C, and the time is 10h.

After the reduction process was completed, the reaction temperature was lowered to the target, and the pressure of the reactor was back-pressurized to 6.0 MPa with 10% (molar ratio) synthesis gas, and then emptied after about 24 hours. The reaction temperature is 220°C, the reaction space velocity is 5000h ^-1 , the working pressure is 6.0MPa, the molar ratio of H ₂ /CO in the synthesis gas is 2, and the product is analyzed by gas chromatography (Shimadzu GC-2014, GC-2010plus) The types and contents of various components contained, and correspondingly calculate the conversion rate and selectivity of the reaction, the reaction results are shown in Table 1 and Table 2.

Table 2 embodiment catalyst reaction product distribution result

From the data in Table 1 and Table 2, it can be seen that synthesis gas can be used to prepare mixed alcohols and aldehydes in one step. By adjusting the catalyst preparation and changing the reaction process conditions, the product distribution can be adjusted freely, as follows: oxygenated compounds (including mixed alcohols and mixed alcohols) Aldehydes) in the total product selectivity between 30% and 70%, and C2 ₊ products in the oxygenate distribution can reach up to more than 90%, the proportion of mixed alcohols in the total oxygenate is between 30% to 70% (the corresponding ratio of mixed aldehydes is between 70% and 30%).

Claims (15)

1. A cobalt-based catalyst for syngas one-step system of mixed alcohols and aldehydes, characterized in that it comprises: Co, Mn, Cu, alkali metals and auxiliary agents; Wherein, the molar ratio of Mn/Co is 0～10; The content of the alkali metal is calculated based on the mass percentage of the alkali metal oxide in the catalyst, and the range y is 0<y≤10%; The molar ratio of Cu/Co ranges from 0 to 10; The auxiliary agent is selected from at least one of transition metals, rare earth metals or alkaline earth metals, and the molar ratio of the auxiliary agent to Co is in the range of 0-10. the 2. cobalt-based catalyst as claimed in claim 1, is characterized in that: the mol ratio of described Mn/Co is 0.5～2; The content of the alkali metal is calculated based on the mass percentage of the alkali metal oxide in the catalyst, and the range y is 0.5%<y≤2%; The molar ratio of Cu/Co ranges from 0.1 to 1; The molar ratio of additives to Co is in the range of 0.1-1. the 3. cobalt-based catalyst as claimed in claim 1, is characterized in that: described alkali metal is selected from the one in Li, Na, K or Cs; Described transition metal comprises: Fe, Ni, Zr, Zn, Ru, Rh or Pd; The rare earth metals include: La or Ce; Alkaline earth metals include: Mg, Ca or Ba. the 4. The cobalt-based catalyst according to claim 3, wherein the alkali metal is Na. the 5. a preparation method of cobalt-based catalyst as described in any one of claim 1-4, is characterized in that, comprises the step: (1) According to the composition ratio of the catalyst, the nitrates of Cu, Co, Mn and additives are prepared into a mixed salt solution; (2) According to the composition ratio of the catalyst, the precipitant containing alkali metal is prepared into a precipitant solution; Wherein, the precipitation agent is selected from at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate or potassium hydroxide; (3) Co-precipitate the mixed salt solution in step (1) and the precipitant solution in step (2) at 10-100°C and pH 6-12; (4) After the precipitation is over, age at 10-100°C for 0.5-24 hours; after the aging, follow the steps (5A) or (5B) below to obtain the catalyst: (5A) After aging, the catalyst is obtained after separation, washing, drying and roasting; (5B) After aging, the precursor of the catalyst is obtained after separation, washing, drying and roasting, and the precursor of the catalyst is impregnated with the above alkali metal solution, dried and roasted to obtain the catalyst. the 6. The method according to claim 5, characterized in that: in the step (1), the molar concentration of the total metal in the mixed salt solution ranges from 0.01 to 10 mol/L. the 7. The method according to claim 5, characterized in that: in the step (2), the precipitating agent is sodium carbonate; the molar concentration of the precipitating agent solution ranges from 0.01 to 10 mol/L. the 8. The method according to claim 5, characterized in that: in the step (3), the mixing volume ratio of the mixed salt solution and the precipitant solution is 1:5-5:1; In step (3), co-precipitate the mixed salt solution in step (1) and the precipitant solution in step (2) at 50-80° C. and pH 7-9. the 9. The method according to claim 8, characterized in that: the mixing volume ratio of the mixed salt solution and the precipitating agent solution is 1:2˜2:1. the 10 . The method according to claim 5 , characterized in that: in the step (4), aging is carried out at 50-80° C. for 1-5 hours. 11 . the 11. The method according to claim 5, characterized in that: in the step (5A) or (5B), the drying temperature is 50-150°C; the drying time is 1-24h; the calcination temperature is 200-800°C; Roasting time is 0.5~24h; In step (5B), the concentration range of the alkali metal solution is 0.1mol/L-4.0mol/L; the impregnation temperature is room temperature, the impregnation time is 1-24h, and the alkali metal solution is impregnated with an equal volume of the catalyst precursor. the 12. The method according to claim 11, characterized in that: in the step (5A) or (5B), the drying temperature is 100-120°C; the drying time is 10-12h; the calcination temperature is 300-400°C; The roasting time is 2 to 5 hours. the In step (5B), the concentration of the alkali metal solution ranges from 0.5 mol/L to 1.0 mol/L. the 13. An application of the cobalt-based catalyst as claimed in any one of claims 1-4, characterized in that: it is used in the catalytic reaction of syngas one-step system of mixed alcohols and aldehydes; Among them, the catalytic reaction conditions are: the reaction temperature is 150-350°C; the working pressure is 0.1-13Mpa; the reaction space velocity is 100-10000h ^-1 ; the synthesis gas is composed of H ₂ and CO, and the ratio of H ₂ /CO The molar ratio is 0.1-10. 14. The application according to claim 13, characterized in that: the conditions of the catalytic reaction are: the reaction temperature is 200-300°C; the working pressure is 2-6Mpa; the reaction space velocity is 2000-6000h ^-1 ; the synthesis gas is It is composed of H ₂ and CO, and the molar ratio of H ₂ /CO is 1-3. 15. The application according to claim 13, characterized in that: the catalyst needs to be activated before it is used in the catalytic reaction of syngas to produce mixed alcohols and aldehydes in one-step method, wherein the activation conditions are: in a dilute hydrogen atmosphere, Heat up to 150-600°C; activate for 1-24 hours; The diluted hydrogen atmosphere is a mixture of hydrogen and inert gas, wherein the molar ratio of hydrogen is 10%-50%; the space velocity of the diluted hydrogen atmosphere is 1000-20000h ^-1 .