CN106607024B - Catalyst for synthesizing oxalate by CO gas phase, preparation method and application - Google Patents
Catalyst for synthesizing oxalate by CO gas phase, preparation method and application Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesizing oxalate by CO gas phase, a preparation method and application thereof, and mainly solves the technical problems of low activity and selectivity and poor stability in the prior art. The catalyst comprises the following components in percentage by weight: a) taking palladium as an active component, and taking the amount of a simple substance as 0.1-4.0% of the weight of the carrier; b) zinc is taken as an auxiliary agent, and the amount of the zinc is 0.05-2.0% of the weight of the carrier by the simple substance; c) rare earth elements are used as modifiers, and the amount of the simple substance is 0.1-3.0% of the weight of the carrier; d) alumina is used as a carrier; the alumina carrier is modified by rare earth elements, and the specific surface area is 3-40 m2The pore volume of the material with the pore diameter of 15-40 nanometers accounts for 75-95% of the total pore volume, so that the problem is solved well, and the material can be used in industrial production of oxalate through CO gas phase synthesis.
Description
Technical Field
The invention relates to a catalyst for synthesizing oxalate by CO gas phase, a preparation method and application thereof.
Background
The oxalate is an important chemical raw material, and can be used for preparing intermediates of oxalic acid, glycol, carbonate, medicaments and dyes, plastic promoters, solvents and the like. The traditional method for synthesizing dimethyl oxalate utilizes esterification reaction of oxalic acid and methanol, wherein oxalic acid, one of main raw materials, is produced by a sodium formate method, carbon monoxide and sodium hydroxide are synthesized into sodium formate at 160 ℃ and 18-20kg of pressure, then the sodium formate is obtained by concentration and dehydrogenation at 400 ℃, lead oxalate is generated by the action of the sodium oxalate and lead sulfate, sulfuric acid is further used for acidification to obtain a crude oxalic acid product, and finally barium carbonate and one percent of polyacrylamide are used for coagulation and precipitation to obtain refined oxalic acid. The synthesis of oxalate by gas-phase catalytic coupling of CO and methyl nitrite opens up a new route for producing oxalic acid from carbon raw material, and the new progress of oxalic acid synthesis is continuously reported abroad since the eighties.
Japanese patent JP 8242656A first discloses a process for synthesizing dimethyl oxalate by using a platinum group metal supported catalyst in which the space-time yield of the catalyst is 432 g/L.h and the yield is not lowered by a 480-hour continuous reaction.
U.S. Pat. No. 4,4334433 discloses Pd-Mo/Al2O3And Pd-Ni/Al2O3Catalyst at normal pressure, 110 deg.C and space velocity of 2000h-1Initial feed gas composition: CH (CH)3ONO-15％、CO-20％、CH3OH-15％、NO-3％、N2At a concentration of-47% (by volume, all gas concentrations hereinafter are referred to as "volume concentration"), the space-time yield of dimethyl oxalate was 400 g/L.h, and the selectivity of dimethyl oxalate from CO reached 95%.
US4507494 discloses a Pd-Ti/Al alloy2O3Catalyst under the pressure of 0.24MPa, at the temperature of 115 ℃ and at the space velocity of 3000h-1Initial feed gas composition: CH (CH)3ONO-10％、CO-20％、CH3OH-4％、NO-3％、N2Under the condition of 63 percent, the reaction is continuously carried out for 950 hours, the space-time yield of the dimethyl oxalate is 429-462 g/L.h, and the selectivity of the dimethyl oxalate formed by CO reaches 95 percent.
Chinese patent CN95116136.9 discloses a catalyst for oxalate synthesis, uses Zr for drilling as an auxiliary agent, and prepares Pd-Zr/Al by an impregnation method2O3A catalyst. The catalyst is adopted to carry out the reaction of synthesizing the oxalate from the CO and the nitrite on a fixed bed reaction device, but the yield of the oxalate of the catalyst is low, the requirement on impurities of raw material gas is higher, the selectivity of the product oxalate is 95 percent, and the conversion per pass of the nitrite is only 64 percent at most.
Thereafter, there are numerous patents reporting the addition of Mo, Ni, Ti, Fe, Ga, Cu, Na, respectively, to the catalyst components2O and SiO2The catalyst composed of the auxiliary agents is applied to the process for synthesizing oxalate from CO and methyl nitrite, but the space-time yield is lower.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the prior art has low activity and selectivity and poor stability, and provides a novel catalyst for synthesizing oxalate by CO gas phase, which has the advantages of high activity and selectivity in the reaction of synthesizing oxalate by using carbon monoxide and nitrite, reasonable bed temperature distribution, tolerance to the influence of impurities such as hydrogen, water vapor and the like, long service life, easy reaction control and the like. The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem. The invention also provides a use of the catalyst corresponding to the solution of the technical problem in the reaction of synthesizing oxalate from CO gas phase.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the catalyst for synthesizing oxalate from CO gas phase comprises a carrier, an active component, an auxiliary agent and/or a modifier, and comprises the following components in percentage by weight:
a) taking palladium as an active component, and taking the amount of a simple substance as 0.1-4.0% of the weight of the carrier;
b) zinc is taken as an auxiliary agent, and the amount of the zinc is 0.05-2.0% of the weight of the carrier by the simple substance;
c) rare earth elements are taken as an auxiliary agent or a modifier, and the amount of a simple substance is 0.1-3.0% of the weight of the carrier;
d) at least one of alumina or silica is used as a carrier.
In the above technical solution, preferably, the alumina carrier is modified by rare earth elements.
In the above technical solution, preferably, the alumina carrier has a specific surface area of 3-40 m2Per gram; more preferably, the alumina support has a specific surface area of 6 to 20 meters2Per gram; most preferably, the alumina support has a specific surface area of 8-10 meters2Per gram.
In the technical scheme, preferably, the pore volume of the alumina carrier with the pore diameter of 15-40 nm accounts for 75-95% of the total pore volume; more preferably, the pore volume of the alumina carrier with the pore diameter of 15 nm-40 nm accounts for 80-90% of the total pore volume
In the technical scheme, the dosage of the active component palladium is preferably 0.3-1.5% of the weight of the carrier calculated by a simple substance; the dosage of the auxiliary agent zinc is preferably 0.1-1.0% of the weight of the carrier calculated by simple substance; the modifier rare earth element is preferably at least one selected from lanthanum and cerium, and the amount of the modifier rare earth element is preferably 0.2-1.5% of the weight of the carrier in terms of simple substance; the alumina carrier is preferably alpha-Al2O3Or preferably alpha-Al2O3And theta-Al2O3In which alpha-Al is present2O3And theta-Al2O3The mass ratio of (A) to (B) is 1 to 30.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of oxalate catalyst for CO gas phase synthesis comprises the following steps:
α-Al2O3a crystal form carrier: treating the formed pseudo-boehmite by steam at the temperature of 700-800 ℃ for 4-8 hours, and then roasting to obtain the pseudo-boehmite; alpha-Al2O3And theta-Al2O3The mixed crystal form carrier of (1): alpha-Al is prepared by roasting pseudo-boehmite powder2O3Mixing the powder with pseudo-boehmite powder according to a certain proportion, forming, treating for 4-8 hours by 700-800 ℃ steam, and roasting for 2-6 hours by 800-950;
(2) preparing a rare earth metal salt into an aqueous solution, and dipping, drying and roasting the alumina carrier prepared in the step (1) in the aqueous solution to obtain a rare earth modified alumina carrier; the rare earth metal salt is selected from at least one of nitrate, acetate, sulfate or citrate of rare earth metal;
(3) preparing a precursor of metal palladium and a salt of metal zinc into an aqueous solution, and dipping, drying and roasting the rare earth modified alumina carrier prepared in the step (2) in the aqueous solution to prepare a catalyst; the precursor of the metal palladium is at least one of halide, nitrate or acetylacetone salt of the palladium; the salt of the metallic zinc is at least one selected from nitrate, sulfate or oxalate of zinc.
The carrier modifier in the technical scheme is as follows: the purpose of changing the surface property and the pore structure of the carrier is achieved by adding a proper amount of rare earth metal oxide on the surface of the carrier, so that the stability and the dispersion of the carrier to active metal are facilitated; and the auxiliary agent: by adding the assistant metal salt into the active metal Pd impregnation liquid and forming a stable mixed solution, the crystal grains of Pd are stabilized in the subsequent roasting process, the interaction force between Pd and a carrier is improved, and the activity of the catalyst is improved.
In the above technical scheme, in the step (2), the organic acid with carbon atom number more than 2 is preferably added into the aqueous solution prepared from the salt of the rare earth metal, so that the pH value of the aqueous solution is 1-5; the organic acid having 2 or more carbon atoms is preferably at least one selected from oxalic acid, succinic acid, citric acid, lactic acid, terephthalic acid, and phytic acid; the preparation method further comprises the step (4): reducing the catalyst for 2-10 hours at the flow rate of 10-150 ml/min/g catalyst and the temperature of 150-400 ℃ by adopting mixed gas, wherein the mixed gas contains inert gas, hydrogen or/and carbon monoxide, the molar content of the hydrogen or/and the carbon monoxide is preferably more than 10%, and the inert gas is preferably at least one selected from nitrogen, carbon dioxide, helium or argon.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the catalyst is used for the reaction of synthesizing oxalate from CO gas phase, the mixed gas containing nitrous acid ester and CO is used as the raw material, the reaction temperature is 80-160 ℃, the volume space velocity is 800--1Under the conditions of reaction pressure of 0.1-1.0MPa and CO/nitrous acid ester molar ratio of 0.5-3.0, the raw material and the catalyst are contacted and reacted to generate the oxalic ester.
In the technical scheme, the reaction temperature is preferably 100--1The reaction pressure is preferably 0.2 to 0.6MPa and the CO/nitrite molar ratio is preferably 1.5 to 2.5.
The reaction of CO and nitrite for synthesizing oxalate is influenced by the dispersion condition of active component Pd on the surface of carrier, specific surface, pore volume and acidity and alkalinity of carrier. The alumina crystal form roasted at high temperature can reduce the acidity and alkalinity of the surface of the carrier, but the surface area of the carrier is lostLarger, not favorable for Pd dispersion. The invention uses alpha-Al2O3And theta-Al2O3The mixed crystal form of (A) is used as a carrier, and can simultaneously achieve the effects of low acidity and alkalinity and small specific surface loss, and obviously improve the performance of the catalyst. In addition, the reaction of synthesizing oxalate from CO and nitrite belongs to a strong exothermic reaction, and the quick evacuation of heat can effectively improve the space-time yield of oxalate and reduce the generation probability of byproducts. By adopting the technology of the invention, the pore volume of the carrier can be effectively modulated, and the carrier with large pore diameter can be obtained, thereby effectively improving the selectivity of the oxalate.
By adopting the technical scheme of the invention, the catalyst has higher activity and selectivity in the reaction of synthesizing dimethyl oxalate from carbon monoxide and methyl nitrite, the reaction temperature is 80-160 ℃, and the volume space velocity is 800--1Under the conditions of reaction pressure of 0.1-1.0MPa and CO/nitrous acid ester mole ratio of 0.5-3.0, the operation is carried out for 3000 hours, the catalyst performance has no decline trend, the space-time yield of dimethyl oxalate is greater than 760 g/L.h, the content of byproduct dimethyl carbonate is less than 2.0%, and the bed layer temperature distribution is reasonable, can resist the influence of impurities such as hydrogen, water vapor and the like, has long service life, is easy to control and obtains better technical effect.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Detailed Description
[ example 1 ]
Treating the formed pseudo-boehmite with water vapor at 750 ℃ for 6-8 hours, and then roasting at 1250 ℃ for 3 hours to obtain alpha-Al2O3An alumina carrier. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.0 wt% Pd +0.25 wt% Zn +0.15 wt% La/Al2O3The catalyst is prepared by the following steps: lanthanum nitrate is selected, impregnation liquid is prepared according to loading capacity, succinic acid is added into the impregnation liquid to control the modification of rare earth metal on the surface of the carrier, the pH value of the solution is 2, and then the specific surface area is 6.84m2Al in g2O3The carrier is soaked in the soaking solution for 1 hour,drying the solid at 110 deg.C for 4 hr, calcining at 400 deg.C for 2 hr, soaking the rare-earth modified carrier in the impregnating solution prepared from palladium chloride and zinc nitrate according to the load of Pd and Zn for 6 hr, drying at 90 deg.C for 3 hr, and calcining at 380 deg.C for 5 hr to obtain Pd-Zn-La/Al2O3Catalyst C1. The catalyst composition and properties are shown in table 1.
[ example 2 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 1: 1 mass ratio, treating for 2 hours by water vapor at 750 ℃, and then roasting for 4 hours at 900 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), 2.0 wt% of Pd +0.5 wt% of Zn +0.7 wt% of La/Al2O3The catalyst is prepared by the following steps: selecting lanthanum acetate, preparing impregnation liquid according to loading capacity, adding succinic acid into the impregnation liquid to control the modification of rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 2, and then enabling the specific surface area to be 8.74m2Al in g2O3Soaking the carrier in soaking liquid for 1 hr, drying the solid at 110 deg.c for 4 hr, roasting at 400 deg.c for 2 hr, soaking the RE modified carrier in soaking liquid comprising Pd chloride and zinc nitrate in the capacity of Pd and Zn for 6 hr, drying at 90 deg.c for 3 hr, and roasting at 380 deg.c for 5 hr to obtain Pd-Zn-La/Al2O3Catalyst C2. The catalyst composition and properties are shown in table 1.
[ example 3 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 7: 1 mass ratio, processing for 3 hours by water vapor at 750 ℃, and then roasting for 5 hours at 850 ℃ to obtain the alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. Weighing 100g of alumina carrier, and calculating by metal simple substance (the same below), according to 0.75 wt% Pd +1.0 wt% Zn +0.85 wt% La +0.55 wt% Ce/Al2O3Content (wt.)The catalyst is prepared by the following specific steps: lanthanum nitrate and cerium sulfate are selected, impregnation liquid is prepared according to loading capacity, in order to control the modification of rare earth metal to the surface of the carrier, terephthalic acid is added into the impregnation liquid, the pH value of the solution is 1, and then the specific surface area is 8.79m2Al in g2O3Soaking the carrier in the soaking liquid for 3 hr, drying the solid at 80 deg.c for 4 hr, roasting at 450 deg.c for 3 hr, soaking the RE modified carrier in the soaking liquid comprising Pd nitrate and zinc sulfate in the amount of Pd and Zn for 3 hr, drying at 100 deg.c for 3 hr, and roasting at 400 deg.c for 6 hr to obtain Pd-Zn-La-Ce/alpha-Al catalyst2O3Catalyst C3. The catalyst composition and properties are shown in table 1.
[ example 4 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 27: 1 mass ratio, treating for 2 hours by water vapor at 750 ℃, and then roasting for 6 hours at 940 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 0.3 wt% Pd +0.5 wt% Zn +1.5 wt% La/Al2O3The catalyst is prepared by the following steps: selecting lanthanum nitrate, preparing impregnation liquid according to loading capacity, adding citric acid into the impregnation liquid to control the modification of the rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 1.5, and then enabling the specific surface area to be 9.88m2Al in g2O3Soaking the carrier in the soaking liquid for 3 hr, drying the solid at 80 deg.c for 4 hr, roasting at 480 deg.c for 4 hr, soaking the RE modified carrier in the soaking liquid comprising Pd acetylacetonate and zinc oxalate for 5 hr, drying at 110 deg.c for 5 hr, and roasting at 420 deg.c for 5 hr to obtain Pd-Zn-La/alpha-Al2O3Catalyst C4. The catalyst composition and properties are shown in table 1.
[ example 5 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder with pseudo-boehmite powderAccording to the weight ratio of 30: 1 mass ratio, treating for 3 hours by water vapor at 750 ℃, and then roasting for 5 hours at 820 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 0.3 wt% Pd +0.7 wt% Zn +0.7 wt% La +0.7 wt% Ce/Al2O3The catalyst is prepared by the following steps: selecting lanthanum citrate and cerium nitrate, preparing impregnation liquid according to loading capacity, adding phytic acid into the impregnation liquid to control the modification of rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 1.3, and then enabling the specific surface area to be 9.96m2Al in g2O3Soaking the carrier in the soaking liquid for 3 hr, drying the solid at 140 deg.c for 12 hr, roasting at 500 deg.c for 4 hr, soaking the RE modified carrier in the soaking liquid comprising Pd nitrate and zinc nitrate in the amount corresponding to the load of Pd and Zn for 5 hr, drying at 100 deg.c for 5 hr, and roasting at 450 deg.c for 6 hr to obtain Pd-Zn-La-Ce/alpha-Al2O3Catalyst C5. The catalyst composition and properties are shown in table 1.
[ example 6 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 20: 1 mass ratio, processing for 3 hours by water vapor at 750 ℃, and then roasting for 6 hours at 950 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.2 wt% Pd +0.5 wt% Zn +0.3 wt% La/Al2O3The catalyst is prepared by the following steps: selecting lanthanum sulfate, preparing impregnation liquid according to loading capacity, adding lactic acid into the impregnation liquid to control the modification of the rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 2.8, and then enabling the specific surface area to be 9.17m2Al in g2O3Soaking the carrier in the soaking solution for 2 hr, drying the solid at 120 deg.c for 10 hr, roasting at 480 deg.c for 4 hr, soaking the RE modified carrier in the soaking solution of Pd and Zn in palladium nitrate and zinc sulfate for 7 hr, drying at 110 deg.c for 5 hr,roasting at 450 deg.c for 6 hr to prepare Pd-Zn-La/alpha-Al2O3Catalyst C6. The catalyst composition and properties are shown in table 1.
[ example 7 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 12: 1 mass ratio, treating for 3 hours by water vapor at 750 ℃, and then roasting for 5 hours at 800 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.5 wt% Pd +0.3 wt% Zn +1.2 wt% La/Al2O3The catalyst is prepared by the following steps: selecting lanthanum acetate, preparing impregnation liquid according to loading capacity, adding lactic acid and phytic acid into the impregnation liquid to control the modification of the rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 3.5, and then enabling the specific surface area to be 9.04m2Al in g2O3Soaking the carrier in the soaking liquid for 2 hr, drying the solid at 130 deg.c for 9 hr, roasting at 520 deg.c for 4 hr, soaking the RE modified carrier in the soaking liquid comprising Pd nitrate and zinc oxalate for 6 hr, drying at 100 deg.c for 4 hr, and roasting at 420 deg.c for 7 hr to obtain Pd-Zn-La/Al2O3Catalyst C7. The catalyst composition and properties are shown in table 1.
[ example 8 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 3: 1 mass ratio, processing for 3 hours by water vapor at 750 ℃, and then roasting for 3 hours at 850 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.0 wt% Pd +0.25 wt% Zn +0.15 wt% La/Al2O3The catalyst is prepared by the following steps: lanthanum nitrate is selected, impregnation liquid is prepared according to the loading amount, succinic acid is added into the impregnation liquid to control the modification of the rare earth metal on the surface of the carrier, the pH value of the solution is 2, and then the specific surface area is8.21m2Al in g2O3Soaking the carrier in soaking liquid for 1 hr, drying the solid at 110 deg.c for 4 hr, roasting at 400 deg.c for 2 hr, soaking the RE modified carrier in soaking liquid comprising Pd chloride and zinc nitrate in the capacity of Pd and Zn for 6 hr, drying at 90 deg.c for 3 hr, and roasting at 380 deg.c for 5 hr to obtain Pd-Zn-La/Al2O3Catalyst C8. The catalyst composition and properties are shown in table 1.
[ example 9 ]
Treating the formed pseudo-boehmite with water vapor at 750 ℃ for 7 hours, and then roasting at 1250 ℃ for 3 hours to obtain alpha-Al2O3An alumina carrier. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.0 wt% Pd +0.25 wt% Zn +0.15 wt% La/Al2O3The catalyst is prepared by the following steps: selecting palladium chloride, zinc nitrate and lanthanum nitrate according to the loading amounts of Pd, Zn and La, preparing an impregnation solution, adding succinic acid into the impregnation solution to enable the pH value of the solution to be 2, and then enabling the specific surface area to be 6.83m2Al in g2O3Soaking the carrier in the soaking solution for 4 hr, drying the solid at 110 deg.C for 4 hr, and calcining at 400 deg.C for 2 hr to obtain Pd-Zn-La/Al2O3Catalyst C9. The catalyst composition and properties are shown in table 1.
[ example 10 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 1: 2, processing the mixture for 3 hours by water vapor at 750 ℃, and then roasting the mixture for 4 hours at 880 ℃ to obtain the alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.5 wt% Pd +0.3 wt% Zn +1.2 wt% La/Al2O3The catalyst is prepared by the following steps: selecting lanthanum acetate, preparing impregnation liquid according to loading capacity, adding lactic acid and phytic acid into the impregnation liquid to control the modification of the rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 3.0, and then enabling the specific surface area to be 8.32m2Al in g2O3Soaking the carrier in the soaking liquid for 3 hr, drying the solid at 110 deg.c for 7 hr, roasting at 500 deg.c for 4 hr, soaking the RE modified carrier in the soaking liquid comprising Pd nitrate and zinc oxalate for 2 hr, drying at 100 deg.c for 4 hr, and roasting at 450 deg.c for 7 hr to obtain Pd-Zn-La/Al2O3Catalyst C10. The catalyst composition and properties are shown in table 1.
[ example 11 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 40: 1 mass ratio, treating for 3 hours by water vapor at 750 ℃, and then roasting for 4 hours at 800 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.5 wt% Pd +0.3 wt% Zn +1.2 wt% La/Al2O3The catalyst is prepared by the following steps: selecting lanthanum acetate, preparing impregnation liquid according to loading capacity, adding lactic acid and phytic acid into the impregnation liquid to control the modification of the rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 3.0, and then enabling the specific surface area to be 7.75m2Al in g2O3Soaking the carrier in the soaking liquid for 3 hr, drying the solid at 100 deg.c for 3 hr, roasting at 480 deg.c for 4 hr, soaking the RE modified carrier in the soaking liquid comprising Pd nitrate and zinc oxalate for 2 hr, drying at 110 deg.c for 4 hr, and roasting at 450 deg.c for 4 hr to obtain Pd-Zn-La/Al2O3Catalyst C11. The catalyst composition and properties are shown in table 1.
[ example 12 ]
Calcining pseudo-boehmite powder at 1250 ℃ for 4 hours to prepare alpha-Al2O3Mixing the powder and pseudo-boehmite powder according to the weight ratio of 12: 1 mass ratio, treating for 3 hours by water vapor at 750 ℃, and then roasting for 5 hours at 800 ℃ to obtain alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), according to 1.5 wt% Pd +0.05 wt% K/Al2O3The catalyst is prepared by the following steps: selecting potassium carbonate and palladium acetate, preparing impregnation liquid according to the loading amount, adding lactic acid and phytic acid into the impregnation liquid to make the pH value of the solution be 3.5, and then setting the specific surface area to be 9.04m2Al in g2O3Soaking the carrier in the soaking solution for 5 hr, drying at 100 deg.c for 4 hr, and roasting at 420 deg.c for 7 hr to obtain Pd-K/Al2O3Catalyst C12. The catalyst composition and properties are shown in table 1.
[ COMPARATIVE EXAMPLE 1 ]
A comparative catalyst, designated D1, was prepared as described in patent CN95116136.9, example 4. The catalyst composition and properties are shown in table 1.
[ COMPARATIVE EXAMPLE 2 ]
Calcining pseudo-boehmite powder at 750 ℃ for 4 hours to prepare theta-Al2O3Calcining pseudo-boehmite powder at 1250 deg.C for 4 hr to obtain alpha-Al2O3And (3) pulverizing. Then adding theta-Al2O3And alpha-Al2O3The powder is prepared by the following steps: mechanically mixed and molded according to the mass ratio of 1, and then roasted for 4 hours at the temperature of 750 ℃ to prepare alpha-Al2O3And theta-Al2O3A mixed crystal alumina support. 100g of alumina carrier is weighed, and calculated by metal simple substance (the same below), 2.0 wt% of Pd +0.5 wt% of Zn +0.7 wt% of La/Al2O3The catalyst is prepared by the following steps: selecting lanthanum acetate, preparing impregnation liquid according to loading capacity, adding succinic acid into the impregnation liquid to control the modification of rare earth metal on the surface of the carrier, enabling the pH value of the solution to be 2, and then enabling the specific surface area to be 7.57m2Al in g2O3Soaking the carrier in soaking liquid for 1 hr, drying the solid at 110 deg.c for 4 hr, roasting at 400 deg.c for 2 hr, soaking the RE modified carrier in soaking liquid comprising Pd chloride and zinc nitrate in the capacity of Pd and Zn for 6 hr, drying at 90 deg.c for 3 hr, and roasting at 380 deg.c for 5 hr to obtain Pd-Zn-La/Al2O3Catalyst D2. The catalyst composition and properties are shown in table 1.
[ example 13 ]
This example illustrates the use of the catalysts obtained in examples 1-11 in the synthesis of dimethyl oxalate from carbon monoxide and methyl nitrite.
40 g of each of the catalysts C1-C11 obtained in examples 1-11 of the present invention was charged into a stainless steel reaction tube having an inner diameter of 20 mm, and reduced with a mixed gas containing 40 mol% hydrogen, 15 mol% carbon monoxide and the balance nitrogen at a flow rate of 50 ml/min. g of catalyst and 240 ℃ for 4 hours. After reduction, carbon monoxide and methyl nitrite are introduced for reaction evaluation. The catalyst is reacted at the temperature of 128 ℃ and the space velocity of the reaction volume of 2800h-1The reaction was carried out under a reaction pressure of 0.25MPa and a CO/methyl nitrite molar ratio of 2: 1. The results of the reaction for 200h are shown in Table 2.
[ COMPARATIVE EXAMPLE 3 ]
40 g of the catalyst obtained in comparative example 1-2 was charged into a stainless steel reaction tube having an inner diameter of 20 mm, and the reaction evaluation was carried out using the same raw materials and conditions as in examples 1-11. The results of the reaction for 200h are shown in Table 2.
[ example 14 ]
This example illustrates the results of experiments conducted under different process conditions in the reaction of carbon monoxide with methyl nitrite to synthesize dimethyl oxalate using the catalyst obtained in example 5.
40 g of the catalyst obtained in example 5 of the present invention was charged in a stainless steel reaction tube having an inner diameter of 20 mm. Reducing the mixed gas at the flow rate of 140 ml/min-g catalyst and 190 ℃ for 8 hours, wherein the mixed gas contains hydrogen with the molar content of 70 percent and the balance of nitrogen. After reduction, carbon monoxide and methyl nitrite are introduced, and the process conditions are changed for testing. The results of the 200h reaction are shown in Table 3.
[ example 15 ]
This example illustrates the results of a 6000 hour test of the catalyst obtained in example 6 in the preparation of ethylene glycol by hydrogenation of oxalate.
40 g of the catalyst obtained in example 6 according to the invention were introduced into a stainless steel reaction tube having an internal diameter of 20 mm. Reducing the mixed gas for 5 hours at the flow rate of 100 ml/min-g catalyst and the temperature of 180 ℃, wherein the mixed gas contains hydrogen with the mol content of 90 percentAnd the balance nitrogen. Introducing carbon monoxide and methyl nitrite after reduction, and leading the mixture to the reactor at the pressure of 0.35MPa, the temperature of 135 ℃ and the space velocity of 4000h-1The reaction was carried out at a CO/methyl nitrite molar ratio of 1.8. The results of the reaction 6000h are shown in Table 4.
[ COMPARATIVE EXAMPLE 4 ]
40 g of the catalyst obtained in comparative example 1 was charged into a stainless steel reaction tube having an inner diameter of 20 mm, and the reaction evaluation was carried out using the same raw materials and conditions as those in example 9. The reaction results are shown in Table 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
Claims (8)
1. The catalyst for synthesizing oxalate from CO gas phase comprises a carrier, an active component, an auxiliary agent and/or a modifier, and comprises the following components in percentage by weight:
a) taking palladium as an active component, wherein the dosage of the palladium is 0.1-4.0% of the weight of the carrier by the simple substance;
b) zinc is taken as an auxiliary agent, and the amount of the zinc is 0.05-2.0% of the weight of the carrier by the elementary substance;
c) rare earth elements are taken as an auxiliary agent or a modifier, and the amount of a simple substance is 0.1-3.0% of the weight of the carrier;
d) alumina is taken as a carrier, and the pore volume of the alumina carrier with the pore diameter of 15-40 nm accounts for 75-95% of the total pore volume; the alumina carrier is alpha-Al2O3And theta-Al2O3In which alpha-Al is present2O3And theta-Al2O3The mass ratio of (A) to (B) is 1-30; the alpha-Al2O3The preparation method of the crystal form carrier comprises the following steps: treating the formed pseudo-boehmite by steam at the temperature of 700-800 ℃ for 4-8 hours, and then roasting to obtain the pseudo-boehmite; alpha-Al2O3And theta-Al2O3The preparation method of the mixed crystal form carrier comprises the following steps: alpha-Al is prepared by roasting pseudo-boehmite powder2O3The powder is mixed with pseudo-boehmite powder according to a certain proportion and formed, treated by water vapor at 800 ℃ for 4-8 hours at 700 ℃ and then roasted at 950 ℃ for 2-6 hours at 800 ℃.
2. The catalyst for CO gas-phase synthesis of oxalate according to claim 1, characterized in that the active component palladium is used in an amount of 0.3% -1.5% by weight of the carrier calculated as a simple substance.
3. The catalyst for CO gas phase synthesis of oxalate according to claim 1, characterized in that the amount of the auxiliary agent zinc is 0.1% -1.0% of the weight of the carrier calculated by simple substance.
4. The catalyst for CO gas phase synthesis of oxalate according to claim 1, wherein the promoter or modifier is at least one rare earth element selected from lanthanum and cerium, and the amount of the rare earth element is 0.2-1.5% of the weight of the carrier in terms of simple substance.
5. The catalyst for CO gas phase synthesis of oxalate according to claim 1, wherein the pore volume of the alumina carrier with pore diameter of 15-40 nm accounts for 80-90% of the total pore volume.
6. The method for preparing the oxalate catalyst for CO gas phase synthesis according to any one of claims 1 to 5, comprising the following steps:
(1)α-Al2O3a crystal form carrier: treating the formed pseudo-boehmite by steam at the temperature of 700-800 ℃ for 4-8 hours, and then roasting to obtain the pseudo-boehmite; alpha-Al2O3And theta-Al2O3The mixed crystal form carrier of (1): alpha-Al is prepared by roasting pseudo-boehmite powder2O3Mixing the powder with pseudo-boehmite powder according to a certain proportion, forming, treating for 4-8 hours by 700-800 ℃ water vapor, and roasting for 2-6 hours at 800-950 ℃;
(2) preparing a rare earth metal salt into an aqueous solution, and dipping, drying and roasting the alumina carrier prepared in the step (1) in the aqueous solution to obtain a rare earth modified alumina carrier; the rare earth metal salt is selected from at least one of nitrate, acetate, sulfate or citrate of rare earth metal;
(3) preparing a precursor of metal palladium and a salt of metal zinc into an aqueous solution, and dipping, drying and roasting the rare earth modified alumina carrier prepared in the step (2) in the aqueous solution to prepare a catalyst; the precursor of the metal palladium is at least one of halide, nitrate or acetylacetone salt of the palladium; the salt of the metallic zinc is at least one selected from nitrate, sulfate or oxalate of zinc.
7. A method for synthesizing oxalate from CO gas phase uses the mixed gas containing nitrous acid ester and CO as raw material, and the reaction temperature is 80-160 ℃, the volume space velocity is 800--1Under the conditions that the reaction pressure is 0.1-1.0MPa and the CO/nitrous acid ester molar ratio is 0.5-3.0, the raw material is contacted with the catalyst of any one of claims 1-5 to react to generate the oxalic ester.
8. The method for CO gas phase synthesis of oxalate according to claim 7, wherein the reaction temperature is 100--1The reaction pressure is 0.2-0.6MPa, and the molar ratio of CO/nitrous acid ester is 1.5-2.5.
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| CN101993361A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing oxalic ester |
| CN101543784B (en) * | 2009-04-28 | 2011-07-20 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN102649056A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling of CO (carbon monoxide) |
| CN102649057A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
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| CN101543784B (en) * | 2009-04-28 | 2011-07-20 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101993361A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing oxalic ester |
| CN102649056A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling of CO (carbon monoxide) |
| CN102649057A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
| CN102649057B (en) * | 2011-02-25 | 2015-01-07 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
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