Carbon monoxide preparation process

Abstract

The invention provides a carbon monoxide preparation process. The carbon monoxide preparation process comprises the following steps: preparing fluorite-structure zirconium oxide as a cracking catalyst, and adding into a photo-thermal reaction kettle; formic acid is continuously introduced into the photo-thermal reaction kettle at a set flow rate; irradiating the photo-thermal reaction kettle by using sunlight to enable the cracking catalyst to obtain a driving temperature; formic acid in the photo-thermal reaction kettle is driven by a cracking catalyst to be cracked to generate a dehydration reaction; and performing calcium oxide adsorption drying on carbon monoxide generated by the dehydration reaction to obtain ultra-high-purity carbon monoxide. According to the carbon monoxide preparation process provided by the invention, sunlight irradiation is utilized to provide heating energy for the cracking catalyst, so that the energy consumption cost can be reduced, and the environmental protection problem caused by a traditional heating mode can be avoided; calcium oxide is used for drying and purifying carbon monoxide, the purity of carbon monoxide can be improved, compared with a traditional gas separation technology, the raw material cost is low, dependence on equipment is small, and the energy-saving and environment-friendly performance of carbon monoxide processing can be further improved.

Description

Technical Field

[0001] The invention belongs to the technical field of carbon monoxide production, and particularly relates to a carbon monoxide preparation process. Background Art

[0002] Carbon monoxide is an essential gas in many high-tech industries, particularly in semiconductor and integrated circuit manufacturing, and metal-organic sources, where ultra-high-purity carbon monoxide with a purity exceeding 99.99% is typically required. Existing methods for producing ultra-high-purity carbon monoxide primarily rely on cryogenic separation and concentrated sulfuric acid dehydration. These methods rely on high-purity raw materials and expensive reaction equipment, and the production process is subject to high energy consumption and significant environmental pressures. Therefore, there is an urgent need to develop green, environmentally friendly, and low-cost processing technologies for producing ultra-high-purity carbon monoxide. Summary of the Invention

[0003] The embodiment of the present invention provides a carbon monoxide preparation process, which aims to reduce the processing cost of ultra-high purity carbon monoxide and promote energy conservation and environmental protection in industrial production.

[0004] To achieve the above object, the technical solution adopted by the present invention is to provide a carbon monoxide preparation process, comprising: Prepare fluorite structure zirconia as a cracking catalyst and add it into the photothermal reactor; Formic acid is continuously introduced into the photothermal reactor at a set flow rate; Using sunlight to irradiate the photothermal reactor to achieve the driving temperature of the cracking catalyst; The formic acid in the photothermal reactor is driven by a cracking catalyst to undergo a dehydration reaction; The carbon monoxide produced by the dehydration reaction is adsorbed and dried on calcium oxide to obtain ultra-high purity carbon monoxide.

[0005] In one possible implementation, preparing fluorite-structured zirconia includes: The zirconium source precursor and the fluorine dopant are mixed evenly and placed in a closed pressure-resistant reactor; The explosion method is used to create a high temperature and high pressure environment in a closed pressure-resistant reactor; The zirconium source precursor and the fluorine dopant react under high temperature and high pressure to obtain fluorite structured zirconium oxide.

[0006] In some embodiments, the zirconium source precursor is zirconium acetate or zirconium nitrate, the fluorine dopant is ammonium fluoride, and the addition ratio of the fluorine dopant is controlled at 5-15 mol%; the ambient pressure of the high temperature and high pressure environment is ≥10 MPa, and the ambient temperature is ≥3000K.

[0007] Exemplarily, the production of fluorite structured zirconia further includes a post-processing step, which includes: The fluorite structure zirconium oxide obtained by the doping reaction is pickled to remove impurities; The fluorite structured zirconia after pickling and impurity removal is calcined at high temperature.

[0008] For example, the pickling and impurity removal solution used is dilute nitric acid or hydrochloric acid; the high-temperature calcination is carried out in an inert atmosphere at a temperature of 500~600℃, and the calcination time is 100~120min.

[0009] In one possible implementation, a TiC / Cu-based photothermal carrier is provided in the photothermal reactor, and a cracking catalyst is attached to the TiC / Cu-based photothermal carrier; wherein the TiC / Cu-based photothermal carrier is used to heat the cracking catalyst to a driving temperature under irradiation of at least 0.5 times the standard sunlight, and the driving temperature is ≥320°C.

[0010] In some embodiments, continuously introducing formic acid into the photothermal reactor at a set flow rate comprises: heating and vaporizing liquid formic acid to obtain gaseous formic acid; Gaseous formic acid is continuously introduced into the photothermal reactor at a set flow rate.

[0011] Exemplarily, the liquid formic acid is crude formic acid with a concentration of 85±2%.

[0012] In some embodiments, drying the carbon monoxide produced by the dehydration reaction by adsorption with calcium oxide comprises: The carbon monoxide produced by the dehydration reaction is passed into the drying tank; Calcium oxide particles are introduced into the drying tank, and the carbon monoxide produced by the dehydration reaction is brought into countercurrent contact with the calcium oxide particles.

[0013] Exemplarily, a lifting mechanism is provided on the drying tank; wherein, the lifting mechanism is used to lift the calcium oxide particles at the bottom of the drying tank to the top of the drying tank and scatter them, so that the calcium oxide particles form a dynamic material curtain that moves continuously from top to bottom in the drying tank, and the carbon monoxide produced by the dehydration reaction passes through the dynamic material curtain from bottom to top.

[0014] The beneficial effect of the carbon monoxide preparation process provided by the present invention is that: compared with the existing technology, the carbon monoxide preparation process of the present invention uses formic acid as a reaction raw material and fluorite-structured zirconia as a cracking catalyst to carry out a formic acid cracking reaction in a photothermal reactor to prepare carbon monoxide. Since the unique lattice oxygen of the fluorite-structured zirconia can effectively exclude the formic acid dehydrogenation intermediate HCOO, thereby blocking the formic acid dehydrogenation reaction path and 100% selecting the dehydration reaction path, thereby avoiding the by-product hydrogen and resulting in a decrease in the purity of carbon monoxide. At the same time, the cracking catalyst can be used to increase the reaction rate, thereby ensuring that ultra-high-purity carbon monoxide with a purity of more than 99.99% can be efficiently obtained.

[0015] During the formic acid cracking reaction, solar radiation is used to provide heating energy to the cracking catalyst, so that the cracking catalyst reaches a driving temperature and drives the formic acid cracking to undergo a dehydration reaction. Compared with traditional electric heating or gas heating methods, this can greatly reduce energy consumption costs and also avoid the environmental pressure brought by traditional heating methods.

[0016] Since the products of the formic acid dehydration reaction are carbon monoxide and water, accompanied by incompletely reacted formic acid, the carbon monoxide discharged from the photothermal reactor after the dehydration reaction is adsorbed and dried with the help of calcium oxide. Calcium oxide can react with residual formic acid to form calcium formate and water. At the same time, calcium oxide can adsorb water molecules and precipitate calcium oxide, thereby achieving the drying and purification of carbon monoxide, which helps to further improve the purity of carbon monoxide. Compared with traditional gas separation technology, the method of using calcium oxide for adsorption drying not only has low raw material costs, but also has low dependence on equipment, which can further improve the energy-saving and environmental protection performance of carbon monoxide processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 A flow chart of a carbon monoxide production process provided by an embodiment of the present invention; Figure 2 This is a flow chart of the process for preparing fluorite structure zirconia in an embodiment of the present invention; Figure 3 This is a schematic diagram of the three-dimensional structure of a drying tank used in an embodiment of the present invention.

[0018] In the figure: 10, drying tank; 100, lifting mechanism. DETAILED DESCRIPTION

[0019] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0020] See also Figure 1 The carbon monoxide production process provided by the present invention is now described. The carbon monoxide production process comprises: Prepare fluorite structure zirconia as a cracking catalyst and add it into the photothermal reactor; Formic acid is continuously introduced into the photothermal reactor at a set flow rate; Using sunlight to irradiate the photothermal reactor to achieve the driving temperature of the cracking catalyst; The formic acid in the photothermal reactor is driven by a cracking catalyst to undergo a dehydration reaction; The carbon monoxide produced by the dehydration reaction is adsorbed and dried on calcium oxide to obtain ultra-high purity carbon monoxide.

[0021] It should be noted that fluorite-structured zirconia (F-ZrO2) is primarily composed of cubic fluorite and can be added to the photothermal reactor in either nanoparticle or powder form. Powder is preferred to increase its specific surface area. Fluorite-structured zirconia was chosen as the cracking catalyst because formic acid cracking has two pathways: a dehydration reaction (HCOOH→CO+H2O) and a dehydrogenation reaction (HCOOH→CO2+H2). Fluorite-structured zirconia's unique lattice oxygen effectively excludes the formic acid dehydrogenation intermediate HCOO, thereby blocking the dehydrogenation pathway and ensuring that the formic acid cracking reaction proceeds 100% along the dehydration pathway. This prevents the production of hydrogen byproduct and maintains carbon monoxide purity.

[0022] Formic acid can flow through the reactor in solution form, driven by the cracking catalyst to initiate a cracking reaction, or it can flow through the reactor in gaseous form, driven by the cracking catalyst to initiate a cracking reaction. Of course, the cracking catalyst needs to reach a driving temperature (needing to be above 250°C) to drive the formic acid cracking reaction, so a heating method is required for the cracking catalyst. Traditional heating methods are electric or gas heating. In this embodiment, solar energy is used to irradiate the photothermal reactor to achieve photothermal heating of the cracking catalyst, thereby achieving zero-energy reaction drive, which not only saves energy costs but also significantly reduces environmental pressure.

[0023] The products of the formic acid dehydration reaction are carbon monoxide and water. Therefore, after the reaction product carbon monoxide is discharged from the photothermal reactor, it is mixed with water molecules and unreacted formic acid molecules, so it needs to be purified to meet the ultra-high purity requirements of carbon monoxide. Traditional carbon monoxide purification methods require the use of cryogenic separation technology due to the presence of impurity gases. The separation process is not only energy-intensive but also produces waste gas and pollutes the environment. In this embodiment, calcium oxide is used to adsorb and dry the reaction product carbon monoxide. Water molecules can be directly adsorbed by the calcium oxide, and formic acid molecules can react with the calcium oxide to form water and calcium formate. The water is again adsorbed by the calcium oxide, and the calcium formate is precipitated. In this way, the carbon monoxide purification process is achieved by calcium oxide adsorption and drying.

[0024] The carbon monoxide preparation process provided in this embodiment, compared with the existing technology, uses formic acid as the reaction raw material and fluorite-structured zirconium oxide as a cracking catalyst to carry out formic acid cracking reaction in a photothermal reactor to prepare carbon monoxide. It can block the formic acid dehydrogenation reaction path and select the dehydration reaction path 100%, thereby avoiding the by-product hydrogen and causing the purity of carbon monoxide to decrease. On this basis, the reaction product carbon monoxide is purified by calcium oxide adsorption drying to obtain ultra-high purity carbon monoxide with a purity of more than 99.99%. Since solar radiation heating is used instead of conventional electric heating or gas heating, it can greatly reduce energy consumption costs and avoid the environmental pressure brought by traditional heating methods. Moreover, the method of using calcium oxide for adsorption drying not only has low raw material costs but also has low dependence on equipment compared to traditional gas separation technology, which can further improve energy saving and environmental protection performance.

[0025] In some embodiments, see Figure 2 , the production of fluorite structure zirconia includes: The zirconium source precursor and the fluorine dopant are mixed evenly and placed in a closed pressure-resistant reactor; The explosion method is used to create a high temperature and high pressure environment in a closed pressure-resistant reactor; The zirconium source precursor and the fluorine dopant react under high temperature and high pressure to obtain fluorite structured zirconium oxide.

[0026] The selection and synthesis of cracking catalysts are crucial. Traditional catalysts used for formic acid cracking include Y-ZrO2 (yttrium-doped zirconium dioxide), TiO2 (titanium dioxide), and Mo2N (molybdenum dinitride). These catalysts lack the ability to inhibit the dehydrogenation reaction pathway during formic acid cracking, so H2 byproducts are often present in the product, affecting the purity of carbon monoxide. This embodiment uses F-ZrO2 (fluorine-doped zirconium dioxide with a fluorite structure). The dense lattice oxygen on its surface can form stable bonds with COOH intermediates, while having a strong expulsion effect on HCOO intermediates. Therefore, it can inhibit the dehydrogenation reaction and ensure that the formic acid cracking proceeds 100% along the dehydration reaction pathway, thereby ensuring the ultra-high purity of the carbon monoxide produced by the formic acid cracking.

[0027] Traditional cracking catalysts such as Y-ZrO2 need to be doped with the flux Y2O3 during synthesis, which will lead to the by-product hydrogen due to factors such as the decomposition of hydrogen-containing precursors or reducing hydrogen-containing gases, thereby affecting the purity of the subsequent formic acid cracking product carbon monoxide. The explosion method used here can utilize the high temperature and high pressure environment generated in the closed pressure-resistant reactor at the moment of the explosion, so that the zirconium source precursor can be instantly decomposed into highly active ZrO2 metastable nanoparticles. At the same time, the fluorine dopant is cracked to release fluoride ions. The explosion shock wave will cause the metastable ZrO2 lattice to be activated to produce a large number of oxygen vacancies, thereby providing structural sites for fluoride ions.

[0028] Fluoride ions enter the ZrO2 lattice by replacing oxygen vacancies, forming a fluorine-doped structure. Due to the instantaneous high temperature of the explosion, ZrO2 will directly form a cubic fluorite phase. The fluorine-doped structure can reduce the oxygen vacancy concentration, thereby inhibiting the transformation of the tetragonal phase to the monoclinic phase during the subsequent cooling process, and obtaining a fluorite-structured zirconia that is stable at room temperature.

[0029] Since insufficient cooling speed will cause phase change volume expansion and destroy the fluorite structure, the cooling process in this embodiment can be carried out at a speed of 10 4 ~10 6 The rapid cooling scheme of K / s can produce a freezing effect on the high-energy metastable structure, which not only maintains the stability of the fluorite structure, but also enables the product to retain small particle size and uniform fluorine distribution, thereby increasing the specific surface area of ​​fluorite-structured zirconia. At the same time, the high pressure generated at the moment of explosion stimulates high-speed airflow to carry away the by-products of the doping reaction and unreacted metals, thereby ensuring the purity of the product; the high specific surface area and high purity of the fluorite-structured zirconia product are conducive to improving the efficiency of catalytic cracking.

[0030] Here, the explosion method is used to directly synthesize pure fluorite-structured zirconia from a zirconium source precursor and a fluorine dopant. The reactor required only needs to ensure airtightness and pressure resistance, and does not require a complex structure, which is conducive to reducing equipment costs. In addition, the explosion method can use electric explosion (using instantaneous large current to explode the metal wire) or explosives (such as nitroglycerin) explosion, which has obvious advantages in energy saving and environmental protection compared to other methods.

[0031] Optionally, in this embodiment, the zirconium source precursor is zirconium acetate or zirconium nitrate, the fluorine dopant is ammonium fluoride, and the addition ratio of the fluorine dopant is controlled at 5-15 mol%; the ambient pressure of the high temperature and high pressure environment is ≥10 MPa, and the ambient temperature is ≥3000K.

[0032] After the zirconium source precursor and the fluorine dopant are fully mixed and ground evenly, a sufficient doping reaction can be carried out in a high-temperature environment of more than 3000K generated at the moment of explosion; in order to ensure the stability of the fluorite phase structure, the addition ratio of the fluorine dopant is controlled to be no less than 5 mol%. At the same time, considering that too much fluorine dopant will cause the fluorite structure to be over-fluorinated and distorted and collapsed, the addition ratio of the fluorine dopant also needs to be controlled to no more than 15 mol%.

[0033] It should be noted that since the explosion can generate an environmental pressure exceeding 10 MPa in the closed pressure-resistant reactor at the moment of explosion, the closed pressure-resistant reactor should have a pressure resistance exceeding the environmental pressure. At the same time, considering safety, the closed pressure-resistant reactor should be equipped with a remote controller to trigger the explosion. In order to avoid the discharge of hydrogen fluoride that may be produced during the fluorination process and pollute the environment, the closed pressure-resistant reactor should also be equipped with an exhaust gas treatment device.

[0034] Some possible implementations, such as Figure 2 As shown, the above-mentioned preparation of fluorite structure zirconia also includes a post-processing step, which includes: The fluorite structure zirconia obtained by the doping reaction is pickled to remove impurities. The pickling can remove unreacted metal impurities and by-product fluoride salts, thereby ensuring the purity of the fluorite structure zirconia.

[0035] The acid-washed and impurity-removed fluorite zirconia is subjected to high-temperature calcination. High-temperature calcination can dry the acid-washed fluorite zirconia. At the same time, since the fluorite zirconia produced by the explosion method is an agglomerated powder, high-temperature calcination can transform the agglomerated powder into a highly dispersible powder, which is conducive to uniform distribution in the photothermal reactor during formic acid cracking. This not only helps to improve the efficiency of solar radiation heating of the cracking catalyst, but also improves the contact between the cracking catalyst and formic acid, thereby improving the utilization rate of the cracking catalyst and the efficiency of the cracking reaction.

[0036] Specifically, the pickling and impurity removal solution used in this embodiment is dilute nitric acid or hydrochloric acid; the high-temperature calcination is carried out in an inert atmosphere at a temperature of 500-600° C. for 100-120 minutes.

[0037] Using dilute nitric acid or hydrochloric acid as a washing liquid to pickle the explosion products helps to improve the removal effect of the by-product fluoride salt, thereby improving the cleanliness of the fluorite structure zirconia; the inert atmosphere can be specifically created by argon. The inert atmosphere is an oxygen-free environment, which can prevent oxygen from invading the crystal lattice to replace fluoride ions during high-temperature calcination, resulting in fluorine loss, and at the same time avoid the problem of oxygen invading to occupy oxygen vacancies and destroying catalytic active sites. Therefore, using an inert atmosphere for high-temperature calcination is beneficial to maintaining the fluorine doping concentration, while inhibiting phase change and improving the stability of fluorite structure zirconia.

[0038] Since the fluorine dopant will accelerate decomposition to produce hydrogen fluoride at a high temperature exceeding 600°C, this will not only lead to fluorine loss and affect the inhibitory effect of fluorite-structured zirconia on the dehydrogenation reaction, but also be detrimental to environmental protection; in addition, further high temperatures such as above 700°C will induce phase change and destroy the stability of the fluorite structure; a calcination environment below 500°C will cause problems such as organic residue and uneven fluorine doping. Therefore, in this embodiment, a calcination temperature of 500~600°C and a calcination time of 100~120min are selected, which is beneficial to improving the structural stability and catalytic activity of fluorite-structured zirconia.

[0039] In some possible implementations, a TiC / Cu-based photothermal carrier is provided in the above-mentioned photothermal reactor, and a cracking catalyst is attached to the TiC / Cu-based photothermal carrier; wherein the TiC / Cu-based photothermal carrier is used to heat the cracking catalyst to a driving temperature under irradiation of at least 0.5 times the standard sunlight, and the driving temperature is ≥320°C.

[0040] TiC (titanium carbide) has broad-spectrum solar light absorption properties. In synergy with the Cu (copper) substrate, it can achieve a solar radiation absorption rate of over 90%, improving the photothermal conversion efficiency. In addition, the efficient thermal conductivity of Cu enables heat to diffuse rapidly to the surface of the cracking catalyst, allowing the cracking catalyst to quickly reach the driving temperature of the formic acid cracking reaction.

[0041] Based on the above, 0.5 times the standard solar radiation can make the cracking catalyst reach a temperature of not less than 320°C. Therefore, most of the sunshine time can meet the demand for solar radiation heating, thereby ensuring the production time.

[0042] The method of heating the cracking catalyst by irradiating the TiC / Cu-based photothermal carrier with sunlight can make full use of natural resources compared to traditional electric heating or gas heating, thereby greatly reducing production energy consumption, and has the advantage of being green and environmentally friendly compared to traditional heating methods.

[0043] In some embodiments, continuously introducing formic acid into the photothermal reactor at a set flow rate comprises: heating and vaporizing liquid formic acid to obtain gaseous formic acid; Gaseous formic acid is continuously introduced into the photothermal reactor at a set flow rate.

[0044] It should be noted that the above-mentioned liquid formic acid is crude formic acid with a concentration of 85±2%. Commercially available formic acid can usually reach a concentration of 85%. Based on the above-mentioned photothermal catalytic cracking reaction method, low-cost crude formic acid can be directly used, thereby greatly reducing production costs. On this basis, by heating and vaporizing the liquid crude formic acid, the formic acid is introduced into the photothermal reactor in a gaseous state. Since the gaseous formic acid can fully contact the cracking catalyst, the efficiency of the formic acid cracking reaction can be improved.

[0045] Some possible implementations include combining Figure 3 It is understood that the carbon monoxide produced by the above dehydration reaction is dried by calcium oxide adsorption, including: The carbon monoxide produced by the dehydration reaction is passed into the drying tank 10; Calcium oxide particles are introduced into the drying tank 10, and the carbon monoxide produced by the dehydration reaction is brought into countercurrent contact with the calcium oxide particles.

[0046] The carbon monoxide produced by the dehydration reaction is mixed with water molecules and formic acid molecules. Calcium oxide is used to adsorb water molecules. At the same time, calcium oxide can also react with formic acid molecules to form calcium formate, thereby purifying the carbon monoxide. Since the carbon monoxide and calcium oxide particles can continuously move in countercurrent contact within the drying tank 10, the contact between the carbon monoxide and the calcium oxide particles can be improved, thereby improving the efficiency and effect of adsorption drying.

[0047] Specifically, such as Figure 3 As shown, the drying tank 10 is provided with a lifting mechanism 100, wherein the lifting mechanism 100 is used to lift the calcium oxide particles at the bottom of the drying tank 10 to the top of the drying tank 10 and scatter them, so that the calcium oxide particles form a dynamic material curtain that moves continuously from top to bottom in the drying tank 10, and the carbon monoxide generated by the dehydration reaction passes through the dynamic material curtain from bottom to top.

[0048] The calcium oxide particles fall from the top of the drying tank 10 due to their own weight, forming a dynamic material curtain. After landing on the bottom of the drying tank 10, they are lifted back to the top of the drying tank 10 by the lifting mechanism 100 and scattered. This allows the calcium oxide particles to circulate within the drying tank 10 and form a dynamic material curtain. On the one hand, this helps to fully utilize the adsorption and drying properties of the calcium oxide particles, and on the other hand, it can reduce the consumption of calcium oxide particles, thereby saving production costs. The carbon monoxide produced by the dehydration reaction passes through the dynamic material curtain in a countercurrent manner within the drying tank 10, thereby ensuring that it can fully contact the calcium oxide particles, thereby improving the adsorption and drying effect, and further ensuring the purity requirements of the carbon monoxide.

[0049] The following is a comparison table of the carbon monoxide purity obtained using a carbon monoxide preparation process provided in this embodiment, the purity of carbon monoxide obtained using Y-ZrO2 as a catalytic cracking agent formic acid and a cryogenic separation method to purify the product, and the purity of carbon monoxide obtained using a concentrated sulfuric acid dehydration method:

[0050] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A process for preparing carbon monoxide, characterized in that: include: Prepare fluorite structure zirconia as a cracking catalyst and add it into the photothermal reactor; Formic acid is continuously introduced into the photothermal reactor at a set flow rate; irradiating the photothermal reactor with sunlight to enable the cracking catalyst to reach a driving temperature; The formic acid in the photothermal reactor is driven to decompose and generate a dehydration reaction by the cracking catalyst; The carbon monoxide produced by the dehydration reaction is adsorbed and dried by calcium oxide to obtain ultra-high purity carbon monoxide.

2. A process for producing carbon monoxide according to claim 1, characterized in that: The preparation of fluorite structure zirconia comprises: The zirconium source precursor and the fluorine dopant are mixed evenly and placed in a closed pressure-resistant reactor; Using an explosion method to create a high-temperature and high-pressure environment in the sealed pressure-resistant reactor; The zirconium source precursor and the fluorine dopant react with each other under the high temperature and high pressure environment to obtain the fluorite structured zirconium oxide.

3. A process for producing carbon monoxide according to claim 2, characterized in that: The zirconium source precursor is zirconium acetate or zirconium nitrate, the fluorine dopant is ammonium fluoride, and the addition ratio of the fluorine dopant is controlled at 5-15 mol%; the ambient pressure of the high temperature and high pressure environment is ≥10 MPa, and the ambient temperature is ≥3000K.

4. A process for producing carbon monoxide according to claim 2, characterized in that: The method of preparing fluorite structure zirconia further includes a post-processing step, which includes: acid-washing the fluorite-structured zirconium oxide obtained by the doping reaction to remove impurities; The fluorite structured zirconia after pickling and impurity removal is calcined at high temperature.

5. A process for producing carbon monoxide according to claim 4, characterized in that: The pickling and impurity removal uses dilute nitric acid or hydrochloric acid as the washing solution; the high-temperature calcination is carried out in an inert atmosphere at a temperature of 500-600° C. for a calcination time of 100-120 minutes.

6. A process for producing carbon monoxide according to claim 1, characterized in that: A TiC / Cu-based photothermal carrier is provided in the photothermal reactor, and the cracking catalyst is attached to the TiC / Cu-based photothermal carrier; wherein the TiC / Cu-based photothermal carrier is used to heat the cracking catalyst to the driving temperature under irradiation of at least 0.5 times the standard sunlight, and the driving temperature is ≥320°C.

7. A process for producing carbon monoxide according to claim 1, characterized in that: The step of continuously introducing formic acid into the photothermal reactor at a set flow rate comprises: heating and vaporizing liquid formic acid to obtain gaseous formic acid; The gaseous formic acid is continuously introduced into the photothermal reactor at a set flow rate.

8. A process for producing carbon monoxide according to claim 7, characterized in that: The liquid formic acid is crude formic acid with a concentration of 85±2%.

9. A process for producing carbon monoxide according to any one of claims 1 to 8, characterized in that: The carbon monoxide generated by the dehydration reaction is dried by calcium oxide adsorption, which comprises: Passing the carbon monoxide produced by the dehydration reaction into a drying tank; Calcium oxide particles are introduced into the drying tank, and the carbon monoxide generated by the dehydration reaction is brought into countercurrent contact with the calcium oxide particles.

10. A process for producing carbon monoxide according to claim 9, characterized in that: The drying tank is provided with a lifting mechanism, wherein the lifting mechanism is used to lift the calcium oxide particles at the bottom of the drying tank to the top of the drying tank and scatter them, so that the calcium oxide particles form a dynamic material curtain that moves continuously from top to bottom in the drying tank, and the carbon monoxide generated by the dehydration reaction passes through the dynamic material curtain from bottom to top.

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