CN109908947B - Catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas and application thereof - Google Patents
Catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas and application thereof Download PDFInfo
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Abstract
A catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas and application thereof relate to acetic acid. The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas consists of zirconium-based solid solution oxide and modified zeolite molecular sieve containing eight-membered rings, wherein the content of the zirconium-based solid solution oxide is 30-80% by mass percent, and the balance is the modified zeolite molecular sieve containing eight-membered ring structures. The zirconium-based solid solution oxide is MOx‑ZrO2Wherein M is at least one of Zn, Al, Ca, Sr, Ba, Ce, Cr, Ti, V, Ga, In and the like, and MO is calculated by mass percentxThe mass fraction of (A) is 1-15%. The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas can be applied to preparation of acetic acid.
Description
Technical Field
The invention relates to acetic acid, in particular to a catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas and application thereof.
Background
Acetic acid is one of the important organic acids, and is mainly used for producing vinyl acetate, acetic anhydride, acetate, cellulose acetate and the like, wherein polyvinyl acetate can be used for preparing films and adhesives and is also a raw material of synthetic fiber vinylon. At present, the methanol homogeneous phase carbonylation route represented by Cativa process of Monsanto and BP company is mainly used for industrial production, and the catalyst system is homogeneous rhodium or iridium complex (adv.Catal.,2010,53, 1). The two processes have high requirements on the reactor, need strong corrosion-resistant materials, and have the problems of high energy consumption for separating products from the catalyst, high price of noble metal catalysts such as rhodium or iridium used by the catalyst and the like. Therefore, a new green, high-stability and high-selectivity acetic acid synthesis method and a catalyst thereof are urgently needed to be searched.
On the other hand, in recent years, methanol vapor phase carbonylation has been attracting attention. Early Fujimoto et al (chem.lett.,1984,2047) reported that methanol can undergo a gas phase carbonylation reaction to produce acetic acid under the catalysis of acidic molecular sieves. However, the acetic acid selectivity is very low in the process, and the catalyst stability is poor, mainly because the active center of the molecular sieve is passivated by water generated by methanol etherification at low temperature, and the methanol is easy to generate carbon deposition on the molecular sieve. Subsequent researchers have conducted related studies around the carbonylation of methanol or dimethyl ether, but the product is predominantly methyl acetate and contains a portion of acetic acid. Recently, Liu et al (Catal. Sci. technol.,2017,7,4818) reported a process for the synthesis of acetic acid from methanol using a highly selective carbonylation of methanol to acetic acid using an H-MOR catalyst, with methanol conversion and acetic acid selectivity reaching 100% and 95%, respectively. Methanol can be converted from synthesis gas, and the process is mature, so that from the synthesis gas, acetic acid can be prepared by an indirect route of a two-step method, namely methanol preparation from the synthesis gas and acetic acid preparation from methanol gas-phase carbonylation. However, the two-step route requires more equipment and large investment. Therefore, the synthesis gas direct method for preparing acetic acid is concerned. However, most of the catalysts for producing acetic acid from synthesis gas reported at present mainly comprise Rh-based catalysts (J.Catal.,1998,180,194; Catal. Total., 2000,63, 453; Catal. Commun.,2006,7,559), but the raw material Rh is expensive, the CO conversion rate is less than 1%, the acetic acid selectivity is about 60%, and the performance needs to be greatly improved.
Disclosure of Invention
The first purpose of the invention is to provide a catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas.
The second purpose of the invention is to provide the application of the catalyst for preparing the acetic acid by the high-selectivity conversion of the synthesis gas in the preparation of the acetic acid.
The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas consists of 30-80% of zirconium-based solid solution oxide and the balance of modified zeolite molecular sieve containing eight-membered ring structure by mass percent.
The zirconium-based solid solution oxide is MOx-ZrO2Wherein M is Zn, Al, Ca, Sr, Ba, Ce, Cr, Ti,At least one of V, Ga, In and the like, In mass percent, MOxThe mass fraction of (A) is 1-15%.
The modified zeolite molecular sieve containing the eight-membered ring structure is at least one of H-MOR, H-ZSM-35, H-ZSM-57, H-ZSM-10, H-ZSM-11 molecular sieves and the like, and the molecular sieves are dealuminized by steam, wherein the atomic ratio of silicon to aluminum of the molecular sieves is 8-80.
The zirconium-based solid solution oxide is prepared by a hydrothermal method, and the preparation method comprises the following specific steps:
1) weighing at least one salt compound of Zn, Al, Ca, Sr, Ba, Ce, Cr, Ti, V, Ga, In and the like according to the components of the catalyst for preparing acetic acid by high-selectivity conversion of the synthesis gas, adding the salt compound into deionized water or an alcohol solvent to prepare a solution with the mass percentage concentration of 0.1-15%, and stirring for 0.5-20 hours to obtain a solution A; the alcohol solvent is C1～C6At least one of the alcohols of (a);
2) weighing and adding metered zirconium salt and complexing agent into the solution A obtained in the step 1) according to the components of the catalyst for preparing acetic acid by high-selectivity conversion of the synthesis gas, and stirring for 5-10 hours; the zirconium salt is at least one of zirconium nitrate, zirconium chloride, zirconyl nitrate, zirconium acetate and the like; the complexing agent is one of triethanolamine, disodium ethylene diamine tetraacetate, citric acid and the like, wherein the molar ratio of the complexing agent to the zirconium salt is (0.5-2): 1;
3) transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment for 12-72 h at 180-240 ℃; carrying out suction filtration, washing and drying on the obtained solid, then placing a sample in a muffle furnace for roasting at the temperature of 300-700 ℃ for 1-10 h, and obtaining a product, namely the zirconium-based solid solution oxide, which is recorded as y% MOx-ZrO2Wherein y is MOxThe mass percentage of (A) is as follows.
The preparation method of the modified zeolite molecular sieve containing the eight-membered ring structure comprises the following steps:
1) putting a measured zeolite molecular sieve containing eight-membered rings into a fixed bed reactor, introducing mixed gas of pyridine and inert gas with the mass percent of 0.1-10% of pyridine, and adsorbing at 50-350 ℃ for 1-24 h, wherein the pyridine isThe volume airspeed of mixed gas of pyridine and inert gas is 500-10000 ml g-1h-1(ii) a Then, sample A after pyridine treatment is treated by 0.05-0.5M NaNO3Treating the aqueous solution at 80 ℃ for 2-8 h, and roasting the obtained solid in a muffle furnace at the temperature of 300-650 ℃ for 3-10 h;
2) using 10% -30% of H for the sample A in the step 1) in a fixed bed reactor2O/N2Heating to 450-750 ℃ in the atmosphere for 3-12H, wherein H2O/N2The volume space velocity of the gas is 500-10000 ml g-1h-1Taking out the mixture and using 0.1-2M NH at 80 DEG C4NO3And (3) carrying out ion exchange on the solution for 2-8 h, filtering, washing with water, and roasting the sample in a muffle furnace at the temperature of 300-650 ℃ for 3-10 h to obtain the modified zeolite molecular sieve containing the eight-membered ring structure and subjected to water vapor dealumination.
The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas can be applied to preparation of acetic acid, the application can adopt a physical mixing or double-bed mode, and the physical mixing or double-bed mode can adopt one of a fixed bed reactor, a slurry bed, a fluidized bed reactor and the like; the reaction conditions for the preparation of acetic acid may be: h in synthesis gas2The volume ratio of the catalyst to CO is 1: 0.5-4, the reaction pressure is 0.5-8 MPa, and the space velocity of the synthesis gas is 500-15000 h-1The reaction temperature is 180-550 ℃, and the reaction time is more than 50 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the process is a new route of a direct method, has simple process, avoids two or more complicated processes, can greatly reduce equipment and reduce cost;
(2) the catalyst for preparing the acetic acid by the high-selectivity conversion of the synthesis gas has better reaction performance, and the selectivity of the acetic acid is higher than 95% under the optimized condition;
(3) the process couples the synthesis gas to prepare methanol and the gas phase carbonylation reaction of methanol, wherein, the zirconium-based solid solution oxide mainly activates CO hydrogenation to generate a methanol intermediate, and the modified zeolite molecular sieve containing eight-membered rings is responsible for catalyzing the intermediate species to further convert and generate acetic acid with high selectivity.
(4) The catalyst for preparing acetic acid by high-selectivity conversion of the synthesis gas has good stability, low price and potential application prospect.
(5) The coordination of the two functional catalysts can promote the selective conversion of the synthesis gas and realize the selective synthesis of the target product.
Detailed Description
The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas and the preparation method thereof provided by the invention are further described in detail below.
Example 1
1.0g of Zn (NO) is weighed3)2·6H2Adding O into 100mL of water, and stirring for 6h at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g triethanolamine for 5h, transferring to a hydrothermal kettle, and carrying out hydrothermal treatment at 180 ℃ for 12 h; filtering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, roasting for 6 hours, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% ZnO-ZrO2。
Weighing 2.0g H-MOR molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Heating the mixed gas to 300 ℃ at the speed of 5 ℃/min for treating for 24h, and then using 0.05M NaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 deg.C for 2H, heating the obtained solid in a muffle furnace at a rate of 5 deg.C/min to 500 deg.C, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2The temperature is raised to 550 ℃ at the speed of 5 ℃/min for treatment for 5 h. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. Then filtering and washing with water, placing the sample in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, roasting for 5H, obtaining the molecular sieve containing the eight-membered ring and subjected to water vapor dealumination, and marking as H-MOR (H-MOR)2O-550)。
1.0g of zirconium-based solid solution oxide 3% ZnO-ZrO was weighed2And 1.0g of steam dealuminated H-MOR (H)2O-550) molecular sieve mixed grinding for 0.5h, and then transferring the sample to a muffle furnace at 2 DEG CHeating to 500 ℃ at a speed of/min, and roasting for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 400 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, which is recorded as 3 percent of ZnO-ZrO2/H-MOR(H2O-550)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 4MPa, and the space velocity of the synthesis gas is 3600h-1H in synthesis gas2The volume ratio of the carbon dioxide to CO is 1: 0.5. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 2
Weighing 0.7g AlCl3Adding 100mL of water, and stirring for 3h at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g of disodium ethylene diamine tetraacetate for 6 hours, transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment for 12 hours at the temperature of 200 ℃; filtering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample in a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, roasting for 8 hours, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% Al2O3-ZrO2。
Weighing 2.0g H-ZSM-35 molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Heating the mixed gas to 200 ℃ at the speed of 5 ℃/min for treating for 12h, and then using 0.05M NaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 deg.C for 2H, heating the obtained solid in a muffle furnace at a rate of 5 deg.C/min to 500 deg.C, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2The temperature is raised to 750 ℃ at the speed of 5 ℃/min for treatment for 12 h. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. Then filtering and washing with water, heating the sample to 500 ℃ at the speed of 5 ℃/min in a muffle furnace and roasting for 5H to obtain the molecular sieve containing the eight-membered ring and dealuminated by water vapor, and marking as H-ZSM-35 (H-ZSM-35)2O-750)。
Weighing 1.0gZirconium-based solid solution oxide 3% Al2O3-ZrO2And 1.0g of steam dealuminated H-ZSM-35 (H)2O-750) molecular sieve, and then transferring the sample into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 400 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, which is recorded as 3% Al2O3-ZrO2/H-ZSM-35(H2O-750)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 230 ℃, the reaction pressure is 4MPa, and the space velocity of the synthesis gas is 3600h-1H in synthesis gas2The volume ratio of the carbon dioxide to CO is 1: 4. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 3
Weighing 1.2g Ca (NO)3)2·4H2Adding O into 100mL of water, and stirring for 12h at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g of citric acid for 10 hours, transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment at 220 ℃ for 36 hours; filtering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, roasting for 10 hours, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% CaO-ZrO2。
Weighing 2.0g H-ZSM-11 molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Heating the mixed gas to 100 ℃ at the speed of 5 ℃/min for treating for 6h, and then using 0.05M NaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 deg.C for 2H, heating the obtained solid in a muffle furnace at a rate of 5 deg.C/min to 500 deg.C, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2The temperature is raised to 650 ℃ at the speed of 5 ℃/min for treatment for 5 h. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. After-filtration and washing with waterHeating the sample to 500 ℃ at the speed of 5 ℃/min in a muffle furnace, and roasting for 5H to obtain the molecular sieve containing the eight-membered ring and subjected to water vapor dealumination, and marking as H-ZSM-11 (H)2O-650)。
1.0g of zirconium-based solid solution oxide 3% CaO-ZrO was weighed2And 1.0g of steam dealuminated H-ZSM-11 (H)2O-650) molecular sieve, and then transferring the sample into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 300 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, which is recorded as 3% CaO-ZrO2/H-ZSM-11(H2O-650)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 350 ℃, the reaction pressure is 6MPa, and the space velocity of the synthesis gas is 3500h-1The volume ratio of H2 to CO in the synthesis gas is 1: 1. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 4
Weighing 0.6g Sr (NO)3)2Adding 100mL of water, and stirring for 5 hours at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g of disodium ethylene diamine tetraacetate for 10 hours, transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment for 72 hours at 220 ℃; filtering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, roasting for 10 hours, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% SrO-ZrO2。
Weighing 2.0g H-ZSM-57 molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Heating the mixed gas to 200 ℃ at the speed of 5 ℃/min for treating for 3h, and then using 0.05M NaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 deg.C for 2H, heating the obtained solid in a muffle furnace at a rate of 5 deg.C/min to 500 deg.C, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2Atmosphere at 5 deg.CThe temperature is increased to 650 ℃ at the speed of/min for 10 hours. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. Then filtering and washing with water, heating the sample to 500 ℃ at the speed of 5 ℃/min in a muffle furnace and roasting for 5H to obtain the molecular sieve containing the eight-membered ring and dealuminated by water vapor, and marking as H-ZSM-57 (H-ZSM-57)2O-650)。
1.0g of zirconium-based solid solution oxide 3% SrO-ZrO was weighed2And 1.0g of steam dealuminated H-ZSM-57 (H)2O-650) molecular sieve, and then transferring the sample into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 300 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, which is recorded as 3 percent SrO-ZrO2/H-ZSM-57(H2O-650)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 300 ℃, the reaction pressure is 6MPa, and the space velocity of the synthesis gas is 2000h-1The volume ratio of H2 to CO in the synthesis gas is 1: 2. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 5
0.6g of Ba (OH) is weighed2·8H2Adding O into 100mL of water, and stirring for 5 hours at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g triethanolamine for 10h, transferring to a hydrothermal kettle, and carrying out hydrothermal treatment at 240 ℃ for 48 h; filtering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, roasting for 5 hours, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% BaO-ZrO2。
Weighing 2.0g H-MOR molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Heating the mixed gas to 200 ℃ at the speed of 5 ℃/min for 6h, and then using 0.05M NaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 deg.C for 2h, and placing the obtained solid in a muffle furnace at 5 ℃Heating to 500 deg.C at a rate of 500 deg.C/min, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2The temperature is raised to 650 ℃ at the speed of 5 ℃/min for 10 h. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. Then filtering and washing with water, heating the sample to 500 ℃ at the speed of 5 ℃/min in a muffle furnace and roasting for 5H to obtain the molecular sieve containing eight-membered rings and subjected to water vapor dealumination, and marking as H-MOR (H-MOR)2O-650)。
1.0g of zirconium-based solid solution oxide 3% BaO-ZrO was weighed2And 1.0g of steam dealuminated H-MOR (H)2O-650) molecular sieve, and then transferring the sample into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 400 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, which is recorded as 3 percent BaO-ZrO2/H-MOR(H2O-650)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 230 ℃, the reaction pressure is 6MPa, and the space velocity of the synthesis gas is 5000h-1The volume ratio of H2 to CO in the synthesis gas is 1: 2. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 6
0.7g of Ce (NO) is weighed3)3·6H2Adding O into 100mL of water, and stirring for 3h at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g of disodium ethylene diamine tetraacetate for 5 hours, transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment for 24 hours at 180 ℃; filtering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample in a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, roasting for 6 hours, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% CeO2-ZrO2。
Weighing 2.0g H-MOR molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Mixed gas of 5Heating to 200 deg.C at a speed of 200 deg.C/min for 18h, and treating the pyridine-treated sample with 0.05M NaNO3Treating the aqueous solution at 80 deg.C for 2H, heating the obtained solid in a muffle furnace at a rate of 5 deg.C/min to 500 deg.C, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2The temperature is raised to 750 ℃ at the speed of 5 ℃/min for treatment for 5 h. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. Then filtering and washing with water, heating the sample to 500 ℃ at the speed of 5 ℃/min in a muffle furnace and roasting for 5H to obtain the molecular sieve containing eight-membered rings and subjected to water vapor dealumination, and marking as H-MOR (H-MOR)2O-750)。
1.0g of zirconium-based solid solution oxide 3% CeO was weighed2-ZrO2And 1.0g of steam dealuminated H-MOR (H)2O-750) molecular sieve, and then transferring the sample into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 400 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, which is recorded as 3% CeO2-ZrO2/H-MOR(H2O-750)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 230 ℃, the reaction pressure is 4.5MPa, and the space velocity of the synthesis gas is 2000h-1And the volume ratio of H2 to CO in the synthesis gas is 1: 1.5. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 7
0.8g Ga (NO) is weighed3)3Adding 100mL of water, and stirring for 3h at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g of citric acid for 5 hours, transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment at 200 ℃ for 24 hours; filtering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, roasting for 6 hours, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% Ga2O3-ZrO2。
Weighing 2.0g H-MOR molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Heating the mixed gas to 200 ℃ at the speed of 5 ℃/min for treating for 12h, and then using 0.05M NaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 deg.C for 2H, heating the obtained solid in a muffle furnace at a rate of 5 deg.C/min to 500 deg.C, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2The temperature is raised to 750 ℃ at the speed of 5 ℃/min for treatment for 5 h. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. Then filtering and washing with water, heating the sample to 500 ℃ at the speed of 5 ℃/min in a muffle furnace and roasting for 5H to obtain the molecular sieve containing eight-membered rings and subjected to water vapor dealumination, and marking as H-MOR (H-MOR)2O-750)。
1.0g of zirconium-based solid solution oxide 3% Ga was weighed2O3-ZrO2And 1.0g of steam dealuminated H-MOR (H)2O-750) molecular sieve, and then transferring the sample into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 400 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, and recording the obtained sample as 3% Ga2O3-ZrO2/H-MOR(H2O-750)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 320 ℃, the reaction pressure is 5MPa, and the space velocity of the synthesis gas is 3000h-1The volume ratio of H2 to CO in the synthesis gas is 1: 0.5. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 8
0.6g of In (NO) was weighed3)3Adding 100mL of water, and stirring for 3h at 30 ℃; then 25.0g Zr (NO) was added3)4·5H2Stirring O and 20.0g of disodium ethylene diamine tetraacetate for 5 hours, transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment for 24 hours at 220 ℃; will getFiltering the obtained solid, washing to be neutral, drying at 120 ℃ overnight, then placing the sample In a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, roasting for 6h, and obtaining the product, namely the zirconium-based solid solution oxide, which is recorded as 3% In2O3-ZrO2。
Weighing 2.0g H-MOR molecular sieve, placing in a fixed bed reactor, and introducing 2% pyridine/N2Heating the mixed gas to 200 ℃ at the speed of 5 ℃/min for treating for 12h, and then using 0.05M NaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 deg.C for 2H, heating the obtained solid in a muffle furnace at a rate of 5 deg.C/min to 500 deg.C, calcining for 5H, and introducing 30% H into the sample in a fixed bed reactor2O/N2The temperature is raised to 750 ℃ at the speed of 5 ℃/min for treatment for 5 h. Taking out, and reacting with 1M NH at 80 deg.C4NO3The solution was ion exchanged for 2 h. Then filtering and washing with water, heating the sample to 500 ℃ at the speed of 5 ℃/min in a muffle furnace and roasting for 5H to obtain the molecular sieve containing eight-membered rings and subjected to water vapor dealumination, and marking as H-MOR (H-MOR)2O-750)。
1.0g of zirconium-based solid solution oxide 3% In was weighed2O3-ZrO2And 1.0g of steam dealuminated H-MOR (H)2O-750) molecular sieve, and then transferring the sample into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing 5% hydrogen-95% argon, heating to 400 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst, which is recorded as 3% In2O3-ZrO2/H-MOR(H2O-750)。
The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 350 ℃, the reaction pressure is 6MPa, and the space velocity of the synthesis gas is 1000h-1The volume ratio of H2 to CO in the synthesis gas is 1: 1. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 9
Catalyst composition and process of preparationThe same as in example 2. The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 310 ℃, the reaction pressure is 5MPa, and the space velocity of the synthesis gas is 2200h-1The volume ratio of H2 to CO in the synthesis gas is 1: 0.5. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Example 10
The catalyst composition and preparation were the same as in example 4. The catalytic conversion reaction of the synthesis gas is carried out in a fixed bed stainless steel high-pressure miniature fixed bed reactor, and the reaction conditions are as follows: the reaction temperature is 3300 ℃, the reaction pressure is 6MPa, and the space velocity of the synthesis gas is 1000h-1The volume ratio of H2 to CO in the synthesis gas is 1: 0.5. The reaction raw materials and the products enter a gas chromatography for on-line analysis through pipeline heat preservation, and the specific catalytic reaction performance is shown in table 1.
Comparative example 1
25.0g of Zr (NO) are weighed out3)4·5H2Adding O and 20.0g of citric acid into 100mL of water, stirring for 5 hours, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment for 24 hours at 220 ℃; filtering the obtained solid, washing to neutrality, drying at 120 ℃ overnight, putting the sample in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, roasting for 6h, and recording the obtained metal oxide as ZrO2。
1.0g of ZrO was weighed2And 1.0g H-MOR molecular sieve, and then the sample is moved into a muffle furnace to be heated to 500 ℃ at the speed of 2 ℃/min and roasted for 10 h. And (3) placing the roasted sample in a tubular furnace, introducing hydrogen, heating to 400 ℃ at the speed of 2 ℃/min, and reducing for 8 h. Tabletting and molding the reduced solid sample to obtain a sample, namely the catalyst which is recorded as ZrO2/H-MOR。
The catalytic reaction was carried out in a fixed bed high pressure microreactor, the reaction conditions and product analysis were the same as in example 1, and the reaction properties are shown in Table 1.
TABLE 1 evaluation results of catalyst Performance in examples 1 to 10 and comparative example 1
Note: c2-4Aliphatic hydrocarbon compounds with carbon numbers of 2, 3 and 4; c5+Is aliphatic hydrocarbon compound with carbon number not less than 5.
Claims (5)
1. The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas is characterized by consisting of zirconium-based solid solution oxide and a modified zeolite molecular sieve containing eight-membered rings, wherein the content of the zirconium-based solid solution oxide is 30-80% by mass percent, and the balance is the modified zeolite molecular sieve containing eight-membered ring structures; the zirconium-based solid solution oxide is MOx-ZrO2Wherein M is at least one of Zn, Al, Ca, Sr, Ba, Ce, Cr, Ti, V, Ga and In percentage by mass, MOxThe mass fraction of (A) is 1-15%; the modified zeolite molecular sieve containing the eight-membered ring structure is at least one of H-MOR, H-ZSM-35, H-ZSM-57, H-ZSM-10 and H-ZSM-11 molecular sieves, and the molecular sieves are subjected to dealumination by steam, wherein the atomic ratio of silicon to aluminum of the molecular sieves is 8-80;
the preparation method of the modified zeolite molecular sieve containing the eight-membered ring structure comprises the following steps:
1) putting a metered zeolite molecular sieve containing eight-membered rings into a fixed bed reactor, introducing a mixed gas of pyridine and inert gas with the mass percent of 0.1-10% of pyridine, and adsorbing at 50-350 ℃ for 1-24 h, wherein the volume space velocity of the mixed gas of pyridine and inert gas is 500-10000 ml g-1 h-1(ii) a Then using 0.05-0.5 MNaNO to treat the sample after pyridine treatment3Treating the aqueous solution at 80 ℃ for 2-8 h, and roasting the obtained solid in a muffle furnace at 300-650 ℃ for 3-10 h to obtain a sample A;
2) using 10% -30% of H for the sample A in the step 1) in a fixed bed reactor2O/N2Heating to 450-750 ℃ in the atmosphere for 3-12H, wherein H2O/N2The volume space velocity of the gas is 500-10000 ml g-1 h-1Taking out the mixture and using 0.1-2M NH at 80 DEG C4NO3Solution ionizationAnd exchanging for 2-8 h, filtering, washing with water, roasting the sample in a muffle furnace at the temperature of 300-650 ℃ for 3-10 h to obtain the modified zeolite molecular sieve containing the eight-membered ring structure and subjected to water vapor dealumination.
2. The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas according to claim 1, wherein the zirconium-based solid solution oxide is prepared by a hydrothermal method, and the preparation steps are as follows:
1) weighing at least one salt compound of Zn, Al, Ca, Sr, Ba, Ce, Cr, Ti, V, Ga and In according to the components of the catalyst for preparing acetic acid by high-selectivity conversion of the synthesis gas, adding the salt compound into deionized water or an alcohol solvent to prepare a solution with the mass percentage concentration of 0.1-15%, and stirring for 0.5-20 hours to obtain a solution A; the alcohol solvent is C1～C6At least one of the alcohols of (a);
2) weighing and adding metered zirconium salt and complexing agent into the solution A obtained in the step 1) according to the components of the catalyst for preparing acetic acid by high-selectivity conversion of the synthesis gas, and stirring for 5-10 hours; the zirconium salt is at least one of zirconium nitrate, zirconium chloride, zirconyl nitrate and zirconium acetate; the complexing agent is one of triethanolamine, disodium ethylene diamine tetraacetate and citric acid, wherein the molar ratio of the complexing agent to the zirconium salt is (0.5-2): 1;
3) transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal treatment for 12-72 h at 180-240 ℃; carrying out suction filtration, washing and drying on the obtained solid, then placing a sample in a muffle furnace for roasting at the temperature of 300-700 ℃ for 1-10 h, and obtaining a product, namely the zirconium-based solid solution oxide, which is recorded as y% MOx-ZrO2Wherein y is MOxThe mass percentage of (A) is as follows.
3. The catalyst for preparing acetic acid by high-selectivity conversion of synthesis gas according to claim 1 is applied to the preparation of acetic acid, and the reaction conditions for preparing the acetic acid are as follows: h in synthesis gas2The volume ratio of the catalyst to CO is 1: 0.5-4, the reaction pressure is 0.5-8 MPa, and the space velocity of the synthesis gas is 500-15000 h-1Reaction temperatureThe reaction time is more than 50h at 180-550 ℃.
4. Use according to claim 3, wherein physical mixing or double bed is used.
5. The use of claim 4, wherein the physical mixing or double bed mode is one of a fixed bed reactor, a slurry bed reactor and a fluidized bed reactor.
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