CN115709072B - Catalyst for preparing acetic acid by catalyzing methanol carbonylation and preparation method and application thereof - Google Patents
Catalyst for preparing acetic acid by catalyzing methanol carbonylation and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing acetic acid by catalyzing methanol carbonylation, which comprises an active component and a carrier, wherein the carrier is a carbon carrier, the active component is a metal oxide compound of Ce, zr and M, the M is at least one of Cu and Ni, the catalyst is expressed as CeZrMOx/C, and x is the number of oxygen atoms required for meeting the oxidation states of the metals Ce, zr and M; the content of Ce is 12% -40%, the content of Zr is 3% -12% and the content of Cu or Ni is 8-20% based on the weight ratio of the carrier. Meanwhile, the invention also discloses a preparation method and application of the catalyst. The catalyst provided by the invention has no halogen addition, small corrosiveness and high selectivity of the target product acetic acid in the process of preparing acetic acid by methanol carbonylation.
Description
Technical Field
The invention belongs to the technical field of preparing acetic acid, and particularly relates to a catalyst for preparing acetic acid by catalyzing methanol carbonylation, and a preparation method and application thereof.
Background
Acetic acid, also called acetic acid, is an important basic organic raw material, and has wide application, and can be used as a raw material for various products such as vinyl acetate, cellulose acetate, terephthalic acid and the like.
The synthesis method of acetic acid mainly comprises the following steps: (1) The methanol carbonylation process uses homogeneous noble metal as main catalyst and iodide as promoter. The method has the advantages of high catalyst price, strong iodine corrosiveness and difficult separation of products and the catalyst. (2) Ethylene oxidation process comprising hydration of ethylene to produce ethanol, which is oxidized to produce acetic acid; ethylene is oxidized to generate acetaldehyde, and the acetaldehyde is oxidized to prepare acetic acid. The method has low equipment investment, but low ethylene conversion rate, and needs a large amount of energy consumption to remove water in the oxidation process; (3) The ethane oxidation method has wide sources of raw materials, but low selectivity and more byproducts; (4) The direct synthesis gas to acetic acid process includes three parts of methanol synthesis, carbonylation and hydrolysis. The method takes single coal or natural gas as raw material, and the carbonylation step is still a homogeneous catalysis method of noble metal and iodide. The technology for preparing the acetic acid by the gas-solid phase methanol carbonylation by adding the non-noble metal and the non-halogen is developed, the problems of corrosiveness, economy and the like in the methanol carbonylation process can be effectively solved, and the technological process of preparing the acetic acid by the synthesis gas through the methanol carbonylation can be further optimized.
In the prior art, when cerium and zirconium are used as auxiliary agents, noble metals are generally used as main active ingredients, so that the cost is high, and when the catalyst is used for preparing acetic acid, methyl iodide is used as the auxiliary agent, so that the catalyst has strong corrosiveness. For example, chinese patent CN108067226a discloses a catalyst for preparing acetic acid by catalytic gas-phase carbonylation of methanol with iridium supported on activated carbon, wherein the active component is iridium, the first auxiliary agent is manganese, and the second auxiliary agent comprises cerium, zirconium, and the like. The catalyst promoter methyl iodide needs to be added into the reaction system, and the main reactor is made of hastelloy because the methyl iodide has strong corrosiveness, and the main product of the system for catalyzing the carbonylation of methanol is methyl acetate, and only a small amount or a small amount of acetic acid exists.
Chinese patent CN111375414a discloses a methanol carbonylation catalyst, the active components are Ni and Cu, the carrier is petroleum coke-based activated carbon, and the catalyst preparation process is complicated although the specific surface area of the catalyst is large and the active components are well dispersed.
CN102847550A discloses a catalyst for preparing acetic acid and methyl acetate by carbonylation of methanol, mordenite is used as a carrier, cuCl 2 Or NiCl 2 Is a catalyst active component. The catalyst has high selectivity in preparing acetic acid and methyl acetate by catalyzing methanol carbonylation, but mordenite has strong acidity, and is easy to dehydrate methanol to generate dimethyl ether and water, the dimethyl ether can reduce the selectivity of target products, and the water can inhibit the methanol carbonylation reaction to be carried out, so that the conversion rate is reduced.
Therefore, the catalyst system for preparing the acetic acid by gas-solid phase methanol carbonylation, which has low acidity, effectively avoids the generation of water, has little halogen-free addition corrosiveness and is simple in preparation method, needs to be developed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing acetic acid by catalyzing methanol carbonylation, and a preparation method and application thereof.
A catalyst for preparing acetic acid by catalyzing methanol carbonylation, the catalyst comprises an active component and a carrier, wherein the carrier is a carbon carrier, the active component is a metal oxide compound of Ce, zr and M, M is at least one of Cu and Ni, the catalyst is expressed as CeZrMOx/C, and x is the number of oxygen atoms required for meeting the oxidation states of the metals Ce, zr and M; the content of Ce is 12% -40%, the content of Zr is 3% -12% and the content of Cu or Ni is 8-20% based on the weight ratio of the carrier. Namely, in the invention, when M is Cu, the content of Cu is 8-20% by weight of the carrier; when M is Ni, the content of Ni is 8-20%; when M is Cu and Ni, the content of Cu is 8-20%, and the content of Ni is 8-20%.
Preferably, the content of Ce is 20% -30%, the content of Zr is 5% -10%, and the content of Cu or Ni is 10-15%. That is, when M is Cu, the content of Cu is 10-15%; when M is Ni, the content of Ni is 10-15%; when M is Cu and Ni, the content of Cu is 10-15%, and the content of Ni is 10-15%.
Preferably, the carrier is any one of graphene, carbon nanotube and activated carbon.
Preferably, the specific surface area of the support is greater than 200m 2 /g。
The preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises the following steps:
(1) Adding the carrier into nitric acid solution, heating and refluxing at 70-150deg.C for 3-14h, filtering, washing with deionized water to neutrality, oven drying, and grinding; then according to 1g: (10-50 mL), adding the carrier treated by nitric acid into acetone or alcohol, and carrying out ultrasonic treatment for 2-6h;
(2) Dissolving metal cerium salt and zirconium salt in acetone or alcohol, stirring and mixing to obtain metal salt mixed solution with the total ion concentration of cerium and zirconium of 0.5-1mol/L, adding the metal salt mixed solution into the solution in the step (1), stirring for 72-120h at room temperature, drying, roasting and grinding to obtain a catalyst precursor loaded with cerium and zirconium;
(3) According to 1g: (20-50) mL, adding the cerium and zirconium loaded catalyst precursor into alcohol, and carrying out ultrasonic treatment for 1-3h to obtain a solution A;
(4) According to 1g: (20-50 mL), adding the salt of the metal M into alcohol, and carrying out ultrasonic treatment for 1-3h to obtain a solution B;
(5) Adding alkali into alcohol, and performing ultrasonic treatment for 1-3h to obtain a solution C; the alkali is NaOH, KOH or ammonia water; the molar ratio of the alkali to the metal M is (4-8): 1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 50-140 ℃, stirring and refluxing for 2-4 hours, filtering, washing to be neutral, drying, roasting, tabletting, forming and screening by a 20-60-mesh sieve.
Preferably, the molar ratio of alkali to metal M is (4.5-6): 1.
preferably, the alcohol is ethanol or ethylene glycol.
Preferably, the concentration of the nitric acid solution is 5-10 mol/L.
Preferably, the conditions of the drying in step (1) are: drying at 60-100deg.C for 8-12 hr; the drying conditions in the step (2) are as follows: drying at 60-80 ℃ for 6-10h, wherein the roasting conditions are as follows: roasting for 5-8h at 300-400 ℃; the drying conditions in the step (6) are as follows: drying at 80-120 deg.c for 6-10 hr, and roasting: roasting for 3-8h at 300-450 ℃.
Preferably, the cerium salt, zirconium salt, salt of metal M is nitrate, chloride or acetate of the corresponding metal.
The method for preparing acetic acid by catalyzing methanol carbonylation by adopting the catalyst comprises the following steps: filling the catalyst into a fixed bed reactor, introducing hydrogen-containing gas for reduction and activation, then introducing CO-containing gas for replacement and cooling to the reaction temperature of 250-350 ℃, and adding methanol liquid for 1-6h -1 Is vaporized at 100-200deg.C and then is carried into a fixed bed reactor by the CO-containing gas at 2MPa to 5MAnd (3) carrying out carbonylation reaction under Pa, wherein the molar ratio of CO to methanol in the reactant is 5-50.
Preferably, the conditions of the reductive activation are: the reduction temperature is 260-400 ℃, the reduction time is 3-8h, the reduction pressure is normal pressure, and the space velocity of the hydrogen-containing gas is 500-5000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen-containing gas is 100% hydrogen or consists of hydrogen with the volume ratio of more than or equal to 5% and the balance of first balance gas, wherein the first balance gas is nitrogen, helium or argon;
the CO-containing gas is 100% CO or consists of CO with the volume ratio of more than or equal to 50% and the balance of second balance gas, wherein the second balance gas is hydrogen, nitrogen, helium or argon.
The invention has the advantages that:
(1) The preparation method of the catalyst provided by the invention is simple and the preparation process is environment-friendly;
(2) The catalyst provided by the invention has no halogen addition, small corrosiveness and high selectivity of the target product acetic acid in the process of preparing acetic acid by methanol carbonylation.
Detailed Description
Example 1
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is Active Carbon (AC), the active component is a metal oxide compound of Ce, zr and Cu, and the catalyst is expressed as CeO 2 -ZrO 2 -CuO/AC, in weight ratio of the support, ce 40%, zr 3% and Cu 20%; the specific surface area of the carrier is 1060m 2 /g。
2. The preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises the following steps:
(1) Adding the active carbon carrier into 5mol/L nitric acid solution, heating and refluxing for 3 hours at 150 ℃, filtering, washing to be neutral by deionized water, drying for 12 hours at 60 ℃, and grinding; then according to 1g: adding the carrier treated by nitric acid into ethanol according to the proportion of 10mL, and carrying out ultrasonic treatment for 2h;
(2) Dissolving cerium nitrate and zirconium nitrate in ethanol, stirring and mixing to obtain cerium,Adding a metal salt mixed solution with the total ion concentration of 0.5mol/L of zirconium into the solution in the step (1), stirring for 72 hours at room temperature, volatilizing the solution to dryness, drying at 60 ℃ for 10 hours, roasting at 300 ℃ for 8 hours in a muffle furnace, and grinding to obtain cerium and zirconium supported catalyst precursor CeO 2 -ZrO 2 /AC；
(3) According to 1g: a catalyst precursor CeO loaded with cerium and zirconium in a proportion of 50mL 2 -ZrO 2 Adding AC into ethanol, and performing ultrasonic treatment for 2 hours to obtain a solution A;
(4) According to 1g:50mL of copper chloride is added into ethanol, and ultrasonic treatment is carried out for 3 hours to obtain a solution B;
(5) Adding ammonia water into ethanol, and performing ultrasonic treatment for 3 hours to obtain a solution C; the molar ratio of the ammonia water to Cu is 8:1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 50 ℃, stirring and refluxing for 2 hours, filtering, washing to be neutral, drying at 80 ℃ for 10 hours, roasting in a muffle furnace at 300 ℃ for 8 hours, tabletting, forming and screening, and sieving by a 20-60-mesh sieve.
Example 2
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is Graphene, the active component is a metal oxide compound of Ce, zr, cu and Ni, and the catalyst is expressed as CeO 2 -ZrO 2 -CuO-NiO/Graphene, in weight ratio of the support, ce content 12%, zr content 12%, cu content 10%, ni content 15%; the specific surface area of the carrier is 740m 2 /g。
2. The preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises the following steps:
(1) Adding the graphene carrier into a 10 mol/L nitric acid solution, heating and refluxing for 3 hours at 70 ℃, filtering, washing to be neutral by deionized water, drying for 8 hours at 100 ℃, and grinding; then according to 1g: adding the carrier treated by nitric acid into acetone according to the proportion of 50mL, and carrying out ultrasonic treatment for 6h;
(2) Will beDissolving cerium chloride and zirconium chloride in acetone, stirring and mixing to obtain a metal salt mixed solution with the total ion concentration of cerium and zirconium being 1mol/L, adding the metal salt mixed solution into the solution in the step (1), stirring at room temperature for 120 hours, volatilizing the solution to dryness, drying at 60 ℃ for 10 hours, roasting at 350 ℃ for 6 hours in a muffle furnace, and grinding to obtain a cerium and zirconium loaded catalyst precursor CeO 2 -ZrO 2 /Graphene；
(3) According to 1g: ratio of 20mL, catalyst precursor CeO loaded with cerium and zirconium 2 -ZrO 2 Adding Graphene into ethylene glycol, and performing ultrasonic treatment for 3 hours to obtain a solution A;
(4) According to 1g: adding copper nitrate and nickel nitrate into glycol according to the proportion of 40mL, and performing ultrasonic treatment for 1h to obtain a solution B;
(5) Adding NaOH into glycol, and performing ultrasonic treatment for 1h to obtain a solution C; the total molar ratio of NaOH to Cu and Ni is 4:1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 140 ℃, stirring and refluxing for 2 hours, filtering, washing to be neutral, drying at 120 ℃ for 6 hours, roasting in a muffle furnace at 450 ℃ for 3 hours, tabletting, forming and screening, and sieving by a 20-40-mesh sieve.
Example 3
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is a Carbon Nano Tube (CNTs), the active component is a metal oxide compound of Ce, zr and Ni, and the catalyst is expressed as CeO 2 -ZrO 2 -NiO/CNTs, in weight ratio of the support, ce content 25%, zr content 5%, ni content 20%; the specific surface area of the carrier is 280m 2 /g。
2. The preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises the following steps:
(1) Adding the carbon nano tube carrier into 8mol/L nitric acid solution, heating and refluxing for 10 hours at 140 ℃, filtering, washing to be neutral by deionized water, drying for 10 hours at 80 ℃, and grinding; then according to 1g: adding the carrier treated by nitric acid into glycol according to the proportion of 20mL, and carrying out ultrasonic treatment for 3h;
(2) Dissolving cerium acetate and zirconium acetate in glycol, stirring and mixing to obtain a metal salt mixed solution with the total ion concentration of cerium and zirconium of 0.8mol/L, adding the metal salt mixed solution into the solution in the step (1), stirring at room temperature for 96 hours, volatilizing the solution to dryness, drying at 70 ℃ for 8 hours, roasting at 400 ℃ for 8 hours in a muffle furnace, and grinding to obtain a catalyst precursor CeO carrying cerium and zirconium 2 -ZrO 2 /CNTs；
(3) According to 1g:30mL of catalyst precursor CeO loaded with cerium and zirconium 2 -ZrO 2 Adding CNTs into glycol, and performing ultrasonic treatment for 1.5h to obtain a solution A;
(4) According to 1g: adding nickel acetate into ethylene glycol according to the proportion of 35mL, and carrying out ultrasonic treatment for 2h to obtain a solution B;
(5) KOH is added into glycol, and ultrasonic treatment is carried out for 2 hours, so as to obtain solution C; the mol ratio of KOH to Ni is 5:1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 110 ℃, stirring and refluxing for 3 hours, filtering, washing to be neutral, drying at 100 ℃ for 10 hours, roasting at 400 ℃ for 3 hours in a muffle furnace, tabletting, forming and screening, and sieving by a 40-60-mesh sieve.
Example 4
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is a Carbon Nano Tube (CNTs), the active component is a metal oxide compound of Ce, zr, cu and Ni, and the catalyst is expressed as CeO 2 -ZrO 2 -CuO-NiO/CNTs, in weight ratio of the support, ce content 20%, zr content 7%, cu content 20%, ni content 20%; the specific surface area of the carrier is 280m 2 /g。
2. The preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises the following steps:
(1) Adding the carbon nano tube carrier into 6mol/L nitric acid solution, heating and refluxing for 8 hours at 150 ℃, filtering, washing to be neutral by deionized water, drying for 12 hours at 75 ℃, and grinding; then according to 1g: adding the carrier treated by nitric acid into ethylene glycol according to the proportion of 25mL, and carrying out ultrasonic treatment for 4h;
(2) Dissolving cerium nitrate and zirconium nitrate in glycol, stirring and mixing to obtain a metal salt mixed solution with the total ion concentration of cerium and zirconium of 0.6mol/L, adding the metal salt mixed solution into the solution in the step (1), stirring at room temperature for 96 hours, volatilizing the solution to dryness, drying at 80 ℃ for 7 hours, roasting at 350 ℃ for 8 hours in a muffle furnace, and grinding to obtain a catalyst precursor CeO carrying cerium and zirconium 2 -ZrO 2 /CNTs；
(3) According to 1g:25mL of catalyst precursor CeO loaded with cerium and zirconium 2 -ZrO 2 Adding CNTs into glycol, and performing ultrasonic treatment for 2 hours to obtain a solution A;
(4) According to 1g: adding copper nitrate and nickel nitrate into glycol according to the proportion of 40mL, and performing ultrasonic treatment for 1.5h to obtain a solution B;
(5) Adding NaOH into glycol, and performing ultrasonic treatment for 2 hours to obtain a solution C; the total mole ratio of NaOH to Cu and Ni is 4.5:1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 80 ℃, stirring and refluxing for 4 hours, filtering, washing to be neutral, drying for 9 hours at 110 ℃, roasting for 5 hours at 400 ℃ in a muffle furnace, tabletting, forming and screening, and sieving by a 40-60-mesh sieve.
Example 5
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is a Carbon Nano Tube (CNTs), the active component is a metal oxide compound of Ce, zr, cu and Ni, and the catalyst is expressed as CeO 2 -ZrO 2 -NiO/CNTs, in weight ratio of the support, ce content 20%, zr content 10%, ni content 8%; the specific surface area of the carrier is 280m 2 /g。
2. The preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises the following steps:
(1) Adding the carbon nano tube carrier into 6mol/L nitric acid solution, heating and refluxing for 14h at 80 ℃, filtering, washing to be neutral by deionized water, drying for 12h at 75 ℃, and grinding; then according to 1g: adding the carrier treated by nitric acid into ethylene glycol according to the proportion of 25mL, and carrying out ultrasonic treatment for 4h;
(2) Dissolving cerium nitrate and zirconium nitrate in glycol, stirring and mixing to obtain a metal salt mixed solution with the total ion concentration of cerium and zirconium of 0.6mol/L, adding the metal salt mixed solution into the solution in the step (1), stirring at room temperature for 96 hours, volatilizing the solution to dryness, drying at 80 ℃ for 6 hours, roasting at 350 ℃ for 5 hours in a muffle furnace, and grinding to obtain a catalyst precursor CeO carrying cerium and zirconium 2 -ZrO 2 /CNTs；
(3) According to 1g:25mL of catalyst precursor CeO loaded with cerium and zirconium 2 -ZrO 2 Adding CNTs into glycol, and performing ultrasonic treatment for 3 hours to obtain a solution A;
(4) According to 1g: adding nickel nitrate into glycol according to the proportion of 40mL, and performing ultrasonic treatment for 1.5h to obtain a solution B;
(5) Adding NaOH into glycol, and performing ultrasonic treatment for 2 hours to obtain a solution C; the molar ratio of NaOH to Ni is 4.5:1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 80 ℃, stirring and refluxing for 4 hours, filtering, washing to be neutral, drying for 9 hours at 110 ℃, roasting for 5 hours at 400 ℃ in a muffle furnace, tabletting, forming and screening, and sieving by a 40-60-mesh sieve.
Example 6
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is Active Carbon (AC), the active component is a metal oxide compound of Ce, zr and Cu, and the catalyst is expressed as CeO 2 -ZrO 2 -CuO/AC, in weight ratio of the support, ce content 20%, zr content 5%, cu content 10%; the specific surface area of the carrier is 1060m 2 /g。
2. In the preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation, in the step (5), the molar ratio of ammonia water to Cu is 4.5:1 otherwise the same as in example 1.
Example 7
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is Active Carbon (AC), the active component is a metal oxide compound of Ce, zr and Cu, and the catalyst is expressed as CeO 2 -ZrO 2 -CuO/AC, in weight ratio of the support, ce content 30%, zr content 10%, cu content 15%; the specific surface area of the carrier is 1060m 2 /g。
2. In the preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation, in the step (5), the molar ratio of ammonia water to Cu is 6:1 otherwise the same as in example 1.
Comparative example 1
The step (6) is as follows: mixing the solution A and the solution B, then dripping the solution C into the mixed solution of the solution A and the solution B at 140 ℃, stirring and refluxing for 2 hours, filtering, washing to be neutral, drying for 6 hours at 120 ℃, roasting for 3 hours at 450 ℃ in a muffle furnace, tabletting, forming, screening, and sieving with a 20-40-mesh sieve, otherwise, the method is the same as that of the example 2.
Comparative example 2
1. The catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises an active component and a carrier, wherein the carrier is Graphene (Graphene), the active component is a metal oxide compound of Cu and Ni, the catalyst is expressed as CuO-NiO/Graphene, and the content of Cu is 10% and the content of Ni is 15% based on the weight ratio of the carrier; the specific surface area of the carrier is 740m 2 /g。
2. The preparation method of the catalyst for preparing acetic acid by catalyzing methanol carbonylation comprises the following steps:
(1) Adding the graphene carrier into a 10 mol/L nitric acid solution, heating and refluxing for 3 hours at 70 ℃, filtering, washing to be neutral by deionized water, drying for 8 hours at 100 ℃, and grinding; then according to 1g: adding the carrier treated by nitric acid into acetone according to the proportion of 50mL, and carrying out ultrasonic treatment for 6h;
(4) According to 1g: adding copper nitrate and nickel nitrate into glycol according to the proportion of 40mL, and performing ultrasonic treatment for 1h to obtain a solution B;
(5) Adding NaOH into glycol, and performing ultrasonic treatment for 1h to obtain a solution C; the total molar ratio of NaOH to Cu and Ni is 4:1, a step of;
(6) Dropwise adding the solution B into the solution C at 140 ℃ for stirring and refluxing for 2 hours, filtering, washing to be neutral, drying at 120 ℃ for 6 hours, roasting in a muffle furnace at 450 ℃ for 3 hours, tabletting, forming and screening, and sieving with a 20-40-mesh sieve.
Application of
The method for preparing acetic acid by catalyzing methanol carbonylation by adopting the catalyst comprises the following steps: filling the catalyst into a fixed bed reactor, introducing hydrogen-containing gas for reduction and activation, then introducing CO for replacement and cooling to the reaction temperature of 250-350 ℃, and adding methanol liquid for 1-6h -1 The space velocity of (2) is gasified at 100-200 ℃ and then is carried into a fixed bed reactor by CO or CO-containing gas, and carbonylation reaction is carried out under 2-5 MPa, wherein the mol ratio of CO to methanol in the reactants is 5-50; the conditions of the reduction activation are as follows: the reduction temperature is 260-400 ℃, the reduction time is 3-8h, the reduction pressure is normal pressure, and the space velocity of the hydrogen-containing gas is 500-5000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen-containing gas is 100% hydrogen or consists of hydrogen with the volume ratio of more than or equal to 5% and the balance of first balance gas, wherein the first balance gas is nitrogen, helium or argon;
the CO-containing gas is 100% CO or consists of CO with the volume ratio of more than or equal to 50% and the balance of second balance gas, wherein the second balance gas is hydrogen, nitrogen, helium or argon;
after 2h of reaction, the product was analyzed on line by gas chromatography, in the present invention, 100% CO was used for the CO-containing gas, and the other reaction conditions and reaction results are shown in Table 1.
TABLE 1 reaction conditions and reaction results for the catalytic carbonylation of methanol to acetic acid
Remarks: other molar selectivities for products other than acetic acid and methyl acetate, including CO 2 Hydrocarbons, methanol, dimethyl ether, and the like.
Claims (10)
1. A catalyst for preparing acetic acid by catalyzing methanol carbonylation is characterized in that: the catalyst comprises an active component and a carrier, wherein the carrier is a carbon carrier, the active component is a metal oxide compound of Ce, zr and M, the M is at least one of Cu and Ni, and the catalyst is represented as CeZrMO x C, x is the number of oxygen atoms required to satisfy the oxidation states of the metals Ce, zr and M; the content of Ce is 12-40%, the content of Zr is 3-12% and the content of Cu or Ni is 8-20% based on the weight ratio of the carrier;
the catalyst is prepared by the following steps:
(1) Adding the carrier into nitric acid solution, heating and refluxing at 70-150deg.C for 3-14h, filtering, washing with deionized water to neutrality, oven drying, and grinding; then according to 1g: (10-50 mL), adding the carrier treated by nitric acid into acetone or alcohol, and carrying out ultrasonic treatment for 2-6h;
(2) Dissolving metal cerium salt and zirconium salt in acetone or alcohol, stirring and mixing to obtain metal salt mixed solution with the total ion concentration of cerium and zirconium of 0.5-1mol/L, adding the metal salt mixed solution into the solution in the step (1), stirring for 72-120h at room temperature, drying, roasting and grinding to obtain a catalyst precursor loaded with cerium and zirconium;
(3) According to 1g: (20-50) mL, adding the cerium and zirconium loaded catalyst precursor into alcohol, and carrying out ultrasonic treatment for 1-3h to obtain a solution A;
(4) According to 1g: (20-50 mL), adding the salt of the metal M into alcohol, and carrying out ultrasonic treatment for 1-3h to obtain a solution B;
(5) Adding alkali into alcohol, and performing ultrasonic treatment for 1-3h to obtain a solution C; the alkali is NaOH, KOH or ammonia water; the molar ratio of the alkali to the metal M is (4-8): 1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 50-140 ℃, stirring and refluxing for 2-4 hours, filtering, washing to be neutral, drying, roasting, tabletting, forming and screening by a 20-60-mesh sieve.
2. The catalyst for catalyzing the carbonylation of methanol to produce acetic acid according to claim 1, wherein: the content of Ce is 20-30%, the content of Zr is 5-10%, and the content of Cu or Ni is 10-15%.
3. The catalyst for catalyzing the carbonylation of methanol to produce acetic acid according to claim 1 or 2, wherein: the carrier is any one of graphene, carbon nano tube and active carbon.
4. A catalyst for catalyzing the carbonylation of methanol to produce acetic acid according to claim 3, wherein: the specific surface area of the carrier is more than 200m 2 /g。
5. The method for preparing the catalyst for preparing acetic acid by catalyzing carbonylation of methanol according to claim 1, which is characterized in that: the method comprises the following steps:
(1) Adding the carrier into nitric acid solution, heating and refluxing at 70-150deg.C for 3-14h, filtering, washing with deionized water to neutrality, oven drying, and grinding; then according to 1g: (10-50 mL), adding the carrier treated by nitric acid into acetone or alcohol, and carrying out ultrasonic treatment for 2-6h;
(2) Dissolving metal cerium salt and zirconium salt in acetone or alcohol, stirring and mixing to obtain metal salt mixed solution with the total ion concentration of cerium and zirconium of 0.5-1mol/L, adding the metal salt mixed solution into the solution in the step (1), stirring for 72-120h at room temperature, drying, roasting and grinding to obtain a catalyst precursor loaded with cerium and zirconium;
(3) According to 1g: (20-50) mL, adding the cerium and zirconium loaded catalyst precursor into alcohol, and carrying out ultrasonic treatment for 1-3h to obtain a solution A;
(4) According to 1g: (20-50 mL), adding the salt of the metal M into alcohol, and carrying out ultrasonic treatment for 1-3h to obtain a solution B;
(5) Adding alkali into alcohol, and performing ultrasonic treatment for 1-3h to obtain a solution C; the alkali is NaOH, KOH or ammonia water; the molar ratio of the alkali to the metal M is (4-8): 1, a step of;
(6) Mixing the solution A and the solution C, dripping the solution B into the mixed solution of the solution A and the solution C at 50-140 ℃, stirring and refluxing for 2-4 hours, filtering, washing to be neutral, drying, roasting, tabletting, forming and screening by a 20-60-mesh sieve.
6. The method for preparing the catalyst for preparing acetic acid by catalyzing the carbonylation of methanol according to claim 5, wherein the method comprises the following steps: the alcohol is ethanol or glycol.
7. The method for preparing the catalyst for preparing acetic acid by catalyzing the carbonylation of methanol according to claim 6, wherein the method comprises the following steps: the concentration of the nitric acid solution is 5-10 mol/L.
8. The method for preparing the catalyst for preparing acetic acid by catalyzing the carbonylation of methanol according to claim 7, wherein the method comprises the following steps: the conditions of the drying in the step (1) are as follows: drying at 60-100deg.C for 8-12 hr; the drying conditions in the step (2) are as follows: drying at 60-80 ℃ for 6-10h, wherein the roasting conditions are as follows: roasting for 5-8h at 300-400 ℃; the drying conditions in the step (6) are as follows: drying at 80-120 deg.c for 6-10 hr, and roasting: roasting for 3-8h at 300-450 ℃.
9. A process for the production of acetic acid by the carbonylation of methanol using the catalyst of claim 1, wherein: the method comprises the following steps: filling the catalyst into a fixed bed reactor, introducing hydrogen-containing gas for reduction and activation, then introducing CO-containing gas for replacement and cooling to the reaction temperature of 250-350 ℃, and adding methanol liquid for 1-6h -1 And (2) gasifying the space velocity of the catalyst at 100-200 ℃ and then introducing the gas containing CO into a fixed bed reactor to carry out carbonylation reaction under 2-5 MPa, wherein the molar ratio of CO to methanol in the reactant is 5-50.
10. The method for preparing acetic acid by catalyzing the carbonylation of methanol according to claim 9, wherein: the conditions of the reduction activation are as follows: the reduction temperature is 260-400 ℃, the reduction time is 3-8h, the reduction pressure is normal pressure, and the airspeed of the hydrogen-containing gas is 500-5000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen-containing gas is 100% hydrogen or consists of hydrogen with the volume ratio of more than or equal to 5% and the balance of first balance gas, wherein the first balance gas is nitrogen, helium or argon;
the CO-containing gas is 100% CO or consists of CO with the volume ratio of more than or equal to 50% and the balance of second balance gas, wherein the second balance gas is hydrogen, nitrogen, helium or argon.
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