CN113509938B - Catalyst for preparing carbon monoxide and method for preparing carbon monoxide by using catalyst - Google Patents
Catalyst for preparing carbon monoxide and method for preparing carbon monoxide by using catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing carbon monoxide, which is prepared by the following method: (1) mixing the carrier Al2O3Equal volume impregnation of Co (NO)3)2Drying the mixed aqueous solution of LiCl and the mixed aqueous solution, and roasting the dried mixed aqueous solution at the temperature of 450-500 ℃ for 3-4 hours; (2) soaking the obtained substance in the step (1) in CuCl in the same volume2And Zn (NO)3)2Drying the mixed ethanol solution, and roasting at the temperature of 600-650 ℃ for 2-3 hours; (3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying the aqueous solution at 130-140 ℃ for 10-12 hours, and then soaking CH in the same volume3And (3) drying the COOK aqueous solution, and roasting at the temperature of 520-550 ℃ for 5-6 hours. The catalyst has high conversion rate, high yield, less side reaction and side product and easy product purification. The invention also discloses a method for preparing carbon monoxide by adopting the catalyst, which is simple to operate, high in yield and suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a catalyst for preparing carbon monoxide and a method for preparing carbon monoxide by using the catalyst.
Background
Carbon monoxide is a basic chemical raw material which plays a very important role in the fields of petrochemical industry, fine chemical industry and organic synthesis, is widely applied in chemical production, is an important raw material for synthesizing a series of basic organic chemical products and intermediates, and can be used for preparing almost all basic chemicals such as ammonia, phosgene, alcohol, acid, anhydride, acyl chloride, ester, lactone, aldehyde, ketone, ether, amine, alkane, olefin and the like from carbon monoxide. In addition, the property of carbon monoxide reacting with transition metal to produce metal carbonyl or metal carbonyl derivative can be used for preparing high-purity metal or various homogeneous reaction catalysts required by organic chemical production.
The industrial production of carbon monoxide on a large scale usually adopts the processes of water gas purification and separation, hydrocarbon catalytic oxidation, carbon dioxide catalytic reduction and the like. For example, CN1275961A discloses a process for the preparation of hydrogen and carbon monoxide using a hydrocarbonaceous material as substrate and a catalyst using a metal from group VIII of the periodic table of the elements as active component to produce hydrogen and carbon monoxide. However, the catalyst used in this method contains noble metal elements, the cost is high, and the product is a mixed gas of hydrogen and carbon monoxide, the separation and purification are difficult, and in addition, the method needs to be operated at a temperature of at least 800 ℃, the conditions are not mild, and the energy consumption is large. In addition, CN109833872A discloses a cobalt oxide bulk phase catalyst with controllable product distribution, and a preparation method and an application thereof, which obtains a mixed gas of carbon monoxide and methane in any ratio by catalytic hydrogenation of carbon dioxide, but the separation of the two is difficult, and it is difficult to obtain a relatively pure carbon monoxide gas.
Therefore, the methods can also simultaneously generate other gases, such as carbon dioxide, hydrogen, oxygen or methane, so that the purity of the carbon monoxide in the prepared product is low, and complicated processes are needed for separation and purification.
In addition, the carbon monoxide is prepared by adopting a formic acid dehydration method in the field, the purity of the carbon monoxide in the gas product prepared by the method is high, the cost of the method is high because a large amount of concentrated sulfuric acid or concentrated phosphoric acid is used for achieving the purpose of dehydration in the reaction, and waste acid generated after the reaction is difficult to treat.
Therefore, the art is also seeking other ways to make carbon monoxide that are simple, efficient, and environmentally friendly. For example, CN109908904A discloses a transition metal monatomic catalyst, and a preparation method and an application thereof, wherein the catalyst uses a transition metal monatomic as an active component, uses carbon black as a carrier, and disperses the transition metal monatomic on the surface and inside of the carbon black, and the reaction is performed to prepare carbon monoxide by electrocatalysis of carbon dioxide. Also, CN1422803A discloses a process for producing high purity carbon monoxide by catalytic decarbonylation of methyl formate or a mixture of methyl formate and methanol as a substrate to produce high purity carbon monoxide and by-product methanol, wherein the catalyst is obtained by supporting an alkali metal fluoride on an alkaline oxide support having a high specific surface area. However, the catalyst used in the method adopts metal villiaumite as an active component, and has the disadvantages of high toxicity, high corrosivity and severe requirements on the material quality of a reactor.
In view of the foregoing, there is a need for a low-cost, simple-reaction, and environmentally friendly technique for producing high-purity carbon monoxide.
Disclosure of Invention
[ problem ] to
In view of the defects in the prior art, an object of the present invention is to provide a catalyst for preparing carbon monoxide, the catalyst uses formic acid as a reactant, can catalyze the reaction of formic acid to generate carbon monoxide and water, has high conversion rate, high yield, less side reactions and byproducts, is easy to purify the product, particularly does not adopt high-pollution and difficult-to-process materials such as concentrated sulfuric acid or concentrated phosphoric acid, is more environment-friendly, and can greatly save the cost by recycling the catalyst.
The invention aims to provide a method for preparing carbon monoxide by adopting the catalyst, which is simple to operate, high in yield and suitable for large-scale industrial production.
[ solution ]
To achieve the above objects, one aspect of the present invention provides a catalyst for producing carbon monoxide, which is prepared by the following method:
(1) adding carrier Al2O3Equal volume impregnation of Co (NO)3)2Drying the mixed aqueous solution of LiCl and the mixed aqueous solution, and then roasting the dried mixed aqueous solution for 3 to 4 hours at the temperature of 450 to 500 ℃;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2And Zn (NO)3)2Drying the mixed ethanol solution, and roasting at the temperature of 600-650 ℃ for 2-3 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying the aqueous solution at 130-140 ℃ for 10-12 hours, and then soaking CH in the same volume3And (3) drying the COOK (potassium acetate) aqueous solution, and roasting at the temperature of 520-550 ℃ for 5-6 hours.
In the present invention, alumina Al is used2O3As a carrier, the catalyst has excellent mechanical strength and chemical inertness, and cannot react with materials in a system, so that the prepared catalyst is not easy to disintegrate and has low loss rate. Also, the catalyst according to the present invention deposits multiple layers of active materials on the carrier by the above method, thereby enabling effective catalytic cracking of formic acid into carbon monoxide and water, which has high catalytic efficiency with less side reactions and by-products.
Preferably, in the step (1), Co (NO) in the mixed aqueous solution3)2The concentration of (A) can be 1.2-1.6 mol/L, the concentration of LiCl can be 1.8-2.4 mol/L, and Co (NO) can be3)2The concentration ratio of the LiCl to the LiCl can be 1: 1.2-1.5.
The drying in the step (1) can be performed at a temperature of 100-120 ℃ for 4-5 hours.
The roasting in the step (1) is preferably carried out at 470-480 ℃ for 3.5-4 hours. Under the calcination conditions, the support can better deposit Co and Li salts.
Preferably, in the step (2), the mixed ethanol solution contains CuCl2The concentration of (b) can be 0.5-0.8 mol/L, Zn (NO)3)2The concentration of (b) can be 0.2-0.4 mol/L, and CuCl2With Zn (NO)3)2The concentration ratio of (A) to (B) may be 1:0.4 to 0.5.
The drying in the step (2) can be carried out at the temperature of 80-100 ℃ for 1-1.5 hours.
The roasting in the step (2) is preferably carried out at the temperature of 620-640 ℃ for 2.5-3 hours. Under the roasting conditions, the carrier can better deposit Cu salt and Zn salt.
Preferably, in the step (3), the CeCl3The concentration of the aqueous solution may be 0.7 to 1.0 mol/L.
The CH3The concentration of the COOK aqueous solution can be 1.5-1.8 mol/L.
In the step (3), CH is impregnated3The subsequent drying of the COOK aqueous solution can be carried out at a temperature of 80-100 ℃ for 4-5 hours.
The roasting in the step (3) is preferably carried out at the temperature of 530-540 ℃ for 5-5.5 hours.
In the catalyst prepared according to the invention, Co and Li are matched with each other to activate a carbon-oxygen single bond between a carbonyl group and a hydroxyl group in a formic acid molecule, the activated formic acid molecule is then subjected to complete breaking of the carbon-oxygen single bond in the presence of Cu and Zn to be separated into a hydroxyl radical and a hydrogen carbonyl radical, Ce and K further catalyze the hydroxyl radical to abstract a hydrogen atom in the hydrogen carbonyl radical to generate a water molecule, and the hydrogen carbonyl radical abstracted from the hydrogen atom is converted into a carbon monoxide molecule, so that the reaction is completed.
Another aspect of the present invention provides a method for preparing carbon monoxide using the above catalyst, the method comprising: formic acid is used as a reactant, the system pressure is 1.0-1.5 MPa, the inlet temperature is 250-280 ℃, the outlet temperature is 200-230 ℃, and the formic acid airspeed is 22-25 h-1In the presence of said catalyst.
Preferably, the method is preferably: formic acid is used as a reactant, and the system pressure is 1.2MPa, the inlet temperature is 260 ℃, the outlet temperature is 220 ℃, and the formic acid space velocity is 23h-1In the presence of said catalyst.
[ advantageous effects ]
In conclusion, the invention has the following beneficial effects:
the catalyst for preparing carbon monoxide according to the present invention deposits multiple layers of active materials on a support, has high catalytic activity, can effectively catalytically crack formic acid into carbon monoxide and water, has high conversion rate and yield, few side reactions and byproducts, and is easy to separate and obtain relatively pure carbon monoxide, and the products are basically carbon monoxide and water. In addition, the reaction adopting the catalyst does not use high-pollution and difficult-to-treat reaction materials such as concentrated sulfuric acid or concentrated phosphoric acid, is more environment-friendly, and can greatly save the cost by recycling the catalyst.
In addition, the method for preparing carbon monoxide by using the catalyst provided by the invention is simple to operate, high in yield and suitable for large-scale industrial production.
Detailed Description
The present invention will be described in further detail with reference to examples.
Sources of materials
Alumina (Al)2O3) From chemical reagents of the national drug group, ltd;
cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) purity 98%, purchased from chemical agents ltd of the national drug group;
lithium chloride (LiCl) with a purity of 99%, available from the national pharmaceutical group chemical agents limited;
cupric chloride (CuCl)2) 98% purity, purchased from Shanghai Aladdin Biotechnology GmbH;
zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) purity 98%, purchased from chemical agents ltd of the national drug group;
cerium chloride (CeCl)3) Purity of 99% and purchased from chemical reagents of national drug group, ltd;
potassium acetate (CH)3COOK), 99% pure, purchased from Shanghai Allantin Biotechnology, Inc.;
formic acid, analytically pure, was purchased from Shanghai Allantin Biotechnology Ltd.
< example >
Example 1
The catalyst for the production of carbon monoxide according to the invention is prepared by the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2A mixed aqueous solution having a concentration of 1.2mol/L and a LiCl concentration of 2.4mol/L, dried at a temperature of 100 ℃ for 5 hours, and then calcined at a temperature of 475 ℃ for 3.5 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.5mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.2mol/L at the temperature of 90 ℃ for 1.5 hours, and then roasting at the temperature of 630 ℃ for 2.5 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying with 0.85mol/L aqueous solution at 135 deg.C for 11 hr, and soaking in equal volume of CH3An aqueous solution having a COOK concentration of 1.65mol/L was dried at a temperature of 90 ℃ for 4.5 hours, and calcined at a temperature of 535 ℃ for 5 hours, thereby obtaining the catalyst.
Example 2
The catalyst for the production of carbon monoxide according to the invention was prepared using the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2Drying a mixed aqueous solution with the concentration of 1.6mol/L and the concentration of LiCl of 2.0mol/L at the temperature of 120 ℃ for 4 hours, and then roasting at the temperature of 470 ℃ for 4 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.8mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.5mol/L at the temperature of 80 ℃ for 1.5 hours, and then roasting at the temperature of 620 ℃ for 3 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying with 0.7mol/L aqueous solution at 130 deg.C for 12 hr, and soaking in equal volume of CH3An aqueous solution having a COOK concentration of 1.5mol/L was dried at a temperature of 80 ℃ for 5 hours, and calcined at a temperature of 530 ℃ for 5.5 hours, thereby obtaining the catalyst.
Example 3
The catalyst for the production of carbon monoxide according to the invention was prepared using the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2A mixed aqueous solution having a concentration of 1.4mol/L and a concentration of LiCl of 2.1mol/L, dried at a temperature of 120 ℃ for 5 hours, and then calcined at a temperature of 480 ℃ for 3.5 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.6mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.3mol/L at the temperature of 100 ℃ for 1 hour, and then roasting at the temperature of 640 ℃ for 2.5 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying in 1.0mol/L aqueous solution at 140 deg.C for 10 hr, and soaking in CH at equal volume3An aqueous solution having a COOK concentration of 1.8mol/L was dried at a temperature of 100 ℃ for 4 hours and calcined at a temperature of 540 ℃ for 5 hours, thereby obtaining the catalyst.
Example 4
The catalyst for the production of carbon monoxide according to the invention was prepared using the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2A mixed aqueous solution having a concentration of 1.2mol/L and a concentration of LiCl of 1.8mol/L, dried at a temperature of 110 ℃ for 4 hours, and then calcined at a temperature of 475 ℃ for 4 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.7mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.3mol/L at the temperature of 80 ℃ for 1 hour, and then roasting at the temperature of 620 ℃ for 3 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying in 0.8mol/L aqueous solution at 130 deg.C for 11 hr, and soaking in equal volume of CH3An aqueous solution of COOK at a concentration of 1.7mol/L, drying at 80 ℃ for 4.5 hours, at 53The catalyst was prepared by calcining at a temperature of 5 ℃ for 5.5 hours.
Example 5
The catalyst for the production of carbon monoxide according to the invention was prepared using the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2Drying a mixed aqueous solution with the concentration of 1.5mol/L and the concentration of LiCl of 2.0mol/L at the temperature of 120 ℃ for 4 hours, and then roasting at the temperature of 470 ℃ for 4 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.65mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.4mol/L at the temperature of 90 ℃ for 1 hour, and then roasting at the temperature of 630 ℃ for 3 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume30.9mol/L aqueous solution, dried at 140 ℃ for 11 hours, after which equal volumes of CH are impregnated3An aqueous solution having a COOK concentration of 1.6mol/L was dried at a temperature of 100 ℃ for 4.5 hours, and calcined at a temperature of 530 ℃ for 5.5 hours, thereby obtaining the catalyst.
Example 6
The catalyst for the production of carbon monoxide according to the invention was prepared using the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2A mixed aqueous solution having a concentration of 1.6mol/L and a LiCl concentration of 2.3mol/L, dried at a temperature of 100 ℃ for 4.5 hours, and then calcined at a temperature of 480 ℃ for 5 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.5mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.4mol/L at the temperature of 100 ℃ for 1.5 hours, and then roasting at the temperature of 640 ℃ for 2.5 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume31.0mol/L aqueous solution, dried at 130 ℃ for 11 hours, and then impregnated with CH in equal volume3An aqueous solution having a COOK concentration of 1.5mol/L was dried at a temperature of 80 ℃ for 4 hours and calcined at a temperature of 540 ℃ for 5 hours, thereby obtaining the catalyst.
Example 7
The catalyst for the production of carbon monoxide according to the invention was prepared using the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2A mixed aqueous solution having a concentration of 1.2mol/L and a LiCl concentration of 2.4mol/L, dried at a temperature of 100 ℃ for 5 hours, and then calcined at a temperature of 475 ℃ for 3.5 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.8mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.5mol/L at the temperature of 80 ℃ for 1.5 hours, and then roasting at the temperature of 620 ℃ for 3 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying with 1.0mol/L aqueous solution at 140 deg.C for 10 hr, and soaking in equal volume of CH3An aqueous solution having a COOK concentration of 1.8mol/L was dried at a temperature of 100 ℃ for 4 hours and calcined at a temperature of 540 ℃ for 5 hours, thereby obtaining the catalyst.
Example 8
The catalyst for the production of carbon monoxide according to the invention is prepared by the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2A mixed aqueous solution having a concentration of 1.4mol/L and a concentration of LiCl of 2.1mol/L, dried at a temperature of 120 ℃ for 5 hours, and then calcined at a temperature of 480 ℃ for 3.5 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.5mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.2mol/L at the temperature of 90 ℃ for 1.5 hours, and then roasting at the temperature of 630 ℃ for 2.5 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3An aqueous solution having a concentration of 0.7mol/L inDrying at 130 ℃ for 12 hours, followed by equal volume impregnation of CH3An aqueous solution having a COOK concentration of 1.5mol/L was dried at a temperature of 80 ℃ for 5 hours, and calcined at a temperature of 530 ℃ for 5.5 hours, thereby obtaining the catalyst.
Example 9
The catalyst for the production of carbon monoxide according to the invention is prepared by the following method:
(1) 10g of carrier Al2O3Equal volume impregnation of Co (NO)3)2Drying a mixed aqueous solution with the concentration of 1.6mol/L and the concentration of LiCl of 2.0mol/L at the temperature of 120 ℃ for 4 hours, and then roasting at the temperature of 470 ℃ for 4 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2The concentration is 0.6mol/L and Zn (NO)3)2Drying the mixed ethanol solution with the concentration of 0.3mol/L at the temperature of 100 ℃ for 1 hour, and then roasting at the temperature of 640 ℃ for 2.5 hours;
(3) immersing the obtained substance in the step (2) in CeCl in the same volume3Drying with 0.85mol/L aqueous solution at 135 deg.C for 11 hr, and soaking in equal volume of CH3An aqueous solution having a COOK concentration of 1.65mol/L was dried at a temperature of 90 ℃ for 4.5 hours, and calcined at a temperature of 535 ℃ for 5 hours, thereby obtaining the catalyst.
Comparative example 1
Using only carrier Al2O3Without supporting any active component to act as a catalyst.
Comparative example 2
Except that step (1) is omitted, the carrier Al is directly adopted2O3A catalyst was obtained in the same manner as in example 1, except that the supporting of step (2) was carried out.
Comparative example 3
A catalyst was produced in the same manner as in example 1, except that the step (2) was omitted and the loading of the step (3) was carried out directly using the resultant of the step (1).
Comparative example 4
A catalyst was obtained in the same manner as in example 1, except that the catalyst obtained in step (2) was used as it was without step (3).
Comparative example 5
Except that Co (NO) is used in the step (1)3)2A catalyst was obtained in the same manner as in example 1 except that impregnation was carried out with a mixed aqueous solution having a concentration of 0.9mol/L and a LiCl concentration of 2.7mol/L, and calcination was carried out at 400 ℃.
Comparative example 6
Except that Co (NO) is used in the step (1)3)2A catalyst was obtained in the same manner as in example 1 except that impregnation was carried out with a mixed aqueous solution having a concentration of 1.9mol/L and a LiCl concentration of 1.5mol/L, and calcination was carried out at 550 ℃.
Comparative example 7
Except that CuCl is adopted in the step (2)2The concentration of Zn (NO) and Zn is 0.2mol/L3)2A catalyst was obtained in the same manner as in example 1, except that the impregnation was performed with a mixed ethanol solution having a concentration of 0.1mol/L and the calcination was performed at 550 ℃.
Comparative example 8
Except that CuCl is adopted in the step (2)2The concentration is 1.1mol/L and Zn (NO)3)2A catalyst was obtained in the same manner as in example 1, except that the impregnation was performed with a mixed ethanol solution having a concentration of 0.6mol/L and the calcination was performed at 700 ℃.
Comparative example 9
Except that CeCl is adopted in the step (3)3The concentration of the aqueous solution is 0.5mol/L, CH3A catalyst was obtained in the same manner as in example 1, except that the concentration of the aqueous COOK solution was 1.2mol/L and that calcination was carried out at 470 ℃.
Comparative example 10
Except that in step (3) the extraction is carried outWith CeCl3The concentration of the aqueous solution is 1.2mol/L, CH3A catalyst was obtained in the same manner as in example 1 except that the concentration of the COOK aqueous solution was 2.0mol/L and that calcination was carried out at 600 ℃.
< test examples >
Formic acid is used as a raw material, and the system pressure is 1.2MPa, the inlet temperature is 260 ℃, the outlet temperature is 220 ℃, and the airspeed of the gaseous formic acid is 23h-1The catalysts prepared in the above examples 1 to 9 and comparative examples 1 to 10 were tested for their effectiveness in catalyzing the production of carbon monoxide, and the results are shown in table 1 below.
[ Table 1]
| Formic acid conversion/% | Carbon monoxide yield/%) | |
| Example 1 | 99.5 | 99.7 |
| Example 2 | 99.2 | 98.5 |
| Example 3 | 97.3 | 99.3 |
| Example 4 | 98.7 | 99.4 |
| Example 5 | 96.4 | 98.1 |
| Example 6 | 98.3 | 98.9 |
| Example 7 | 99.5 | 98.6 |
| Example 8 | 96.1 | 99.2 |
| Example 9 | 97.9 | 98.5 |
| Comparative example 1 | 10.4 | 21.5 |
| Comparative example 2 | 35.8 | 33.2 |
| Comparative example 3 | 42.6 | 38.1 |
| Comparative example 4 | 28.9 | 25.2 |
| Comparative example 5 | 74.1 | 88.5 |
| Comparative example 6 | 70.6 | 82.1 |
| Comparative example 7 | 68.4 | 86.3 |
| Comparative example 8 | 55.3 | 93.2 |
| Comparative example 9 | 75.2 | 80.6 |
| Comparative example 10 | 64.7 | 84.1 |
In table 1 above, the formic acid conversion (%) shows the molar ratio of formic acid to be reacted to the total amount of formic acid used, and the carbon monoxide yield (%) shows the molar ratio of carbon monoxide generated by the catalytic reaction to formic acid to be reacted.
Referring to table 1 above, the catalysts prepared according to examples 1 to 9 of the present invention have very excellent catalytic performance, the formic acid conversion rate can be more than 96%, and the carbon monoxide yield can be as high as more than 98%, indicating that the catalyst of the present invention has high specificity and catalytic effectiveness. In addition, the reaction for preparing the carbon monoxide does not need too high temperature, the catalytic process can be completed at the temperature of 200-300 ℃, the system pressure is low and is only 1.0-1.5 MPa, and the reaction condition is mild, and a high-temperature and high-pressure environment is not needed, so that the method is very favorable for large-scale industrial production.
In contrast, the catalysts obtained in comparative examples 1 to 4, which omit part or all of the active component used in the present invention, cause a decrease in catalytic activity in the form of a cliff, and are no longer suitable as catalysts, show that the catalytic cracking of formic acid and the efficient production of carbon monoxide can be effectively achieved only in the presence of Co, Li, Cu, Zn, Ce and K used in the present invention. Also, as can be seen from the catalysts obtained in comparative examples 5 to 10, even when Co, Li, Cu, Zn, Ce and K were used as active components, it was difficult to achieve good formic acid conversion and carbon monoxide yield when the amounts of these components were outside the ranges defined in the present invention.
In summary, the technical effects of extremely excellent formic acid conversion rate and carbon monoxide yield can be achieved only by using the catalyst in the range of the elements and the amount thereof defined in the present invention.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (6)
1. A catalyst for the production of carbon monoxide, wherein the catalyst is produced by a process comprising:
(1) adding carrier Al2O3Equal volume impregnation of Co (NO)3)2Drying the mixed aqueous solution of LiCl and the mixed aqueous solution, and roasting the dried mixed aqueous solution at the temperature of 450-500 ℃ for 3-4 hours;
(2) soaking the obtained substance in the step (1) in CuCl in the same volume2And Zn (NO)3)2Drying the mixed ethanol solution, and roasting at the temperature of 600-650 ℃ for 2-3 hours;
(3) subjecting the product obtained in step (2)Isovolumetric impregnation of CeCl3Drying the aqueous solution at 130-140 ℃ for 10-12 hours, and then soaking CH in the same volume3Drying COOK aqueous solution, and roasting at 520-550 ℃ for 5-6 hours;
in the step (1), Co (NO) in the mixed aqueous solution3)2Has a concentration of 1.2 to 1.6mol/L, a concentration of LiCl of 1.8 to 2.4mol/L, and Co (NO)3)2The concentration ratio of the LiCl to the LiCl is 1: 1.2-1.5;
in the step (2), CuCl is added into the mixed ethanol solution2In a concentration of 0.5 to 0.8mol/L, Zn (NO)3)2The concentration of (b) is 0.2-0.4 mol/L, and CuCl2With Zn (NO)3)2The concentration ratio of (A) to (B) is 1: 0.4-0.5;
in the step (3), the CeCl3The concentration of the aqueous solution is 0.7 to 1.0mol/L, and the CH3The concentration of the COOK aqueous solution is 1.5-1.8 mol/L.
2. The catalyst according to claim 1, wherein the drying in the step (1) is performed at a temperature of 100 to 120 ℃ for 4 to 5 hours, and the calcination is performed at a temperature of 470 to 480 ℃ for 3.5 to 4 hours.
3. The catalyst according to claim 1, wherein the drying in the step (2) is performed at a temperature of 80 to 100 ℃ for 1 to 1.5 hours, and the calcination is performed at a temperature of 620 to 640 ℃ for 2.5 to 3 hours.
4. The catalyst according to claim 1, wherein in the step (3), CH is impregnated3And after the COOK aqueous solution is dried at the temperature of 80-100 ℃ for 4-5 hours, and the roasting is carried out at the temperature of 530-540 ℃ for 5-5.5 hours.
5. A process for the preparation of carbon monoxide using the catalyst of any one of claims 1 to 4, wherein the process comprises:
the system pressure is 1.0-1.5 MPa, the inlet temperature is 250-280 ℃, the outlet temperature is 200-230 ℃, and the space velocity of formic acid is 22-25 h-1In the presence of said catalyst.
6. The method of claim 5, wherein the method is carried out at a system pressure of 1.2MPa, an inlet temperature of 260 ℃, an outlet temperature of 220 ℃, and a formic acid space velocity of 23h-1In the presence of said catalyst to produce carbon monoxide.
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