WO2011150834A1 - 用于co气相偶联合成草酸酯的规整催化剂及其制备方法与应用 - Google Patents

用于co气相偶联合成草酸酯的规整催化剂及其制备方法与应用 Download PDF

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WO2011150834A1
WO2011150834A1 PCT/CN2011/075018 CN2011075018W WO2011150834A1 WO 2011150834 A1 WO2011150834 A1 WO 2011150834A1 CN 2011075018 W CN2011075018 W CN 2011075018W WO 2011150834 A1 WO2011150834 A1 WO 2011150834A1
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Prior art keywords
catalyst
carrier
coating
oxalate
active component
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English (en)
French (fr)
Inventor
马新宾
赵玉军
王保伟
王胜平
吕静
李振花
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Tianjin University
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Tianjin University
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Priority claimed from CN2010101915809A external-priority patent/CN101850273B/zh
Priority claimed from CN201010191579.6A external-priority patent/CN101851160B/zh
Application filed by Tianjin University filed Critical Tianjin University
Priority to IN99CHN2013 priority Critical patent/IN2013CN00099A/en
Priority to JP2013512744A priority patent/JP5947792B2/ja
Priority to US13/701,508 priority patent/US20130150617A1/en
Publication of WO2011150834A1 publication Critical patent/WO2011150834A1/zh
Anticipated expiration legal-status Critical
Priority to US15/003,804 priority patent/US20160136622A1/en
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    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J37/02—Impregnation, coating or precipitation
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Definitions

  • the invention relates to the synthesis of oxalates, in particular to a regular catalyst for synthesizing oxalates by CO gas phase coupling and a preparation method thereof, and a production method for synthesizing oxalate by gas phase coupling using the structured catalyst ⁇ CO.
  • oxalate is one of the core technologies of "ethylene glycol for coal or natural gas".
  • oxalate slabs are important organic chemical raw materials used in fine chemicals for the preparation of various dyes, pharmaceuticals, important solvents, extractants and various intermediates.
  • the traditional oxalate production process has high cost, high energy consumption, serious pollution, and unreasonable utilization of raw materials.
  • the more advanced synthesis method is alcohol oxidative carbonylation, especially in CO gas phase catalytic coupling to oxalate system, introducing oxygen carrier nitrite (RONO, R is alkane group) in the gas phase alcohol oxidative carbonylation process. , allowing the reaction to proceed under mild conditions.
  • Nitric oxide produced during the reaction process reacts with alcohol and oxygen to form nitrite.
  • the whole process forms a self-closing cycle and no three wastes.
  • the reaction equation is as follows - synthesis reaction: 2RONO f2CO ⁇ (COOR) 2 2 O
  • the method has the advantages of wide source of raw materials, good atomic economy, mild reaction conditions, low energy consumption, no pollution in process, high product selectivity and good product quality.
  • the process route is a clean production process with obvious economic and social benefits. It has received widespread attention and attention at home and abroad. At this stage, countries are in the stage of research or industrial development. In recent years, many scholars at home and abroad have made some progress in the selection of catalysts, activity and carrier effects, and process conditions. However, due to the widespread use of noble metal Pd as the active component of the catalyst, the catalyst is expensive and the oxalate is increased. The production cost makes the economics of the process route lower.
  • the structured honeycomb catalyst has regular parallel longitudinal passages, small pressure drop, suitable for operation at high space velocity, and has the characteristics of small reactor volume, integral assembly, easy replacement, good mass transfer effect, low load, high activity, etc.
  • its application research in gas-solid and gas-liquid-solid multiphase reactions has received more and more attention.
  • the study of structured catalysts has not been reported in the literature. Summary of the invention
  • An object of the present invention is to provide a structured catalyst for CO gas phase coupling synthesis of oxalate, which has the characteristics of high catalytic activity and low cost.
  • the introduction of a new process route for the synthesis of oxalates from coal or natural gas routes has helped to promote the engineering of CO coupled synthetic oxalate technology.
  • Another object of the present invention is to provide a method for preparing a structured catalyst for CO gas phase coupling synthesis of oxalate, which is prepared by dip coating, using alkali treatment and treatment in a hydrogen or CO atmosphere.
  • the catalytic activity of the CO coupled synthetic oxalate catalyst is effectively improved.
  • the active component of the catalyst is confined in the carrier coating. Since the coating is extremely thin, the diffusion resistance is effectively reduced, the mass transfer efficiency of the reaction material between the gas-solid or gas-liquid solid phase is increased, and the reaction material is increased.
  • the contact area with the catalyst greatly improves the catalytic ability of the active component.
  • a further object of the present invention is to provide a process for the production of oxalate by gas phase coupling from a CO using a structured catalyst.
  • a structured catalyst instead of a conventional particle catalyzed hydrazine to synthesize an oxalate production process facilitates a reduction in the pressure drop of the catalyst bed, thereby contributing to further increasing the productivity of the synthetic oxalate single set of equipment. At the same time, it also reduces the loss caused by the catalyst during the filling and use, and reduces the cost of using the catalyst.
  • the invention has the characteristics of high catalytic activity, low cost, convenient and quick replacement, and the like, and is beneficial to the large-scale engineering application.
  • the conventional structure catalyst for CO gas phase coupling synthesis of oxalate provided by the invention is a ceramic peak or a metal honeycomb as a skeleton carrier, a metal oxide as a carrier coating, and a noble metal Pt, Pd, Ir, Rh As an active component, it is made of Fe, Co, Ni as an auxiliary agent;
  • Specific preparation steps mixing a metal nitrate, hydroxide or oxide with dilute nitric acid, and ball milling in a ball mill to obtain a ball-grinding rubber for coating a carrier, which is immersed in a ceramic honeycomb or metal honeycomb carrier by means of dip 3 ⁇ 4 ⁇ 4
  • the carrier coating is loaded, dried, calcined in a muffle furnace to form a metal oxide support coating, and then placed in the precursor solution of the active component and the auxiliary agent, and the active component and the auxiliary agent are loaded by dipping, after drying.
  • Metal oxide coating according to the present invention is divided into the group Al 2 3 ⁇ 4, Si0 2, Zr0 2, TiG) 2, Fe 2 0 3, La 2 0 3, CuO, ZnO, Cr 2 0 3, GaO, BaO, One or more of CaO, MgO, MnO. Or
  • the metal oxide coating composition of the present invention is Al 2 ⁇ 3 ⁇ 4, Si (3 ⁇ 4, Zr(3 ⁇ 4, Ti0 2 , Fe 2 ⁇ 3 ⁇ 4, La 2 ⁇ 3 ⁇ 4, CuO, ZnO, Cr 2 ⁇ 3 ⁇ 4, GaO, One or more of BaO, CaO.
  • the active ingredient of the present invention is one or more of Pt, Pd, Ir, Rh.
  • the auxiliary agent for the structured structure catalyst for CO gas phase coupling synthesis of oxalic acid according to the present invention is one or more of Fe, Co, and Ni.
  • the auxiliaries of the catalyst for the regular structure of CO gas phase coupling synthesis of oxalate according to the present invention further include Cu or Ce.
  • the carrier coating of the catalyst for the regular structure of CO gas phase coupling synthesis oxalate of the present invention accounts for 5-50% by weight of the honeycomb carrier, and the catalyst active component accounts for 0.1-5% of the weight of the carrier coating 1:
  • the catalyst aid comprises 0.03-10 ⁇ by weight of the washcoat.
  • the atomic ratio of the active component to the auxiliary agent is 0.01-5.
  • the ruthenium-containing carrier coating for the regular structure of the CO gas phase coupling synthesis oxalate of the present invention accounts for 5-50% by weight of the honeycomb carrier, and the catalyst active component accounts for 0.1-5% by weight of the carrier coating.
  • the auxiliary agent is 0.3-10% by weight of the carrier coating, and the atomic ratio of the active component to the auxiliary agent is 0.1-5.
  • the carrier coating of the catalyst for the regular structure of CO gas phase coupling synthesis oxalate of the present invention accounts for 5-30% by weight of the honeycomb carrier, and the catalyst active component accounts for 0, 1-2% of the weight of the carrier coating. Catalyst aids account for the weight of the carrier coating 0.3-6%, the atomic ratio of active component to auxiliary is 0.1-3.
  • the present invention provides a method for preparing a conventional structured catalyst for CG) gas phase coupled synthesis of oxalate, characterized in that the specific steps included are;
  • Ball Milling 3 ⁇ 4 Preparation of Glue: Mixing one or more metal nitrates, hydroxides or oxides, adding dilute nitric acid, controlling the enthalpy value of 1-4, after ball milling for 1-48 hours by ball milling a ball-milling gel for coating a carrier;
  • the ceramic honeycomb carrier or the metal honeycomb carrier is subjected to a carrier coating load by dip coating using the above-mentioned ball-grinding glue, and then dried; after one or more dip coatings until the load reaches the requirement, finally in the muffle
  • the furnace is calcined at 900-1300 ° C for 1-12 hours to form a carrier coating;
  • the carrier having the coating structure is placed in the precursor solution of one or more active components and auxiliaries, and the loading of the active components and auxiliaries is carried out by dipping, drying After drying, it is treated under a 3 ⁇ 4 or CO atmosphere for 1-10 hours to prepare the inventive catalyst.
  • the method for preparing the above-mentioned structured catalyst provided by the present invention comprises the steps of:
  • the carrier coating load of the cordierite ceramic honeycomb carrier or the metal honeycomb carrier is carried out by dip coating using the above-mentioned ball-milling rubber, and then dried under the conditions of 70-13 CTC for 2-4 hours, and in the muffle The furnace is fired at 900-120 (TC conditions for 1-12 hours to form a washcoat with a coating loading of 5-50 wt.% of the honeycomb support. To achieve high loading of the coating, multiple dip coatings must be used.
  • the carrier having the coating structure is placed in the precursor solution of one or more active components and auxiliary agents, and the active component and the auxiliary agent are loaded by the dipping method, and the immersion time is 3 minutes - 12 hours.
  • the impregnated honeycomb catalyst is dried at 70 to 13 CTC for 1 to 12 hours, and finally the inventive catalyst is obtained at 400 to 80 (TC for 1 to 10 hours) under a CO atmosphere.
  • the carrier coating after the loading of the active component and the auxiliary agent is dried and then treated with an alkali solution having a concentration of 0.01-2 M for 0.5 to 24 hours;
  • the alkali solution is one or more of NaOH, KOH, a 2 C0 3 , K 2 C0 3 , NaHC ⁇ 3 ⁇ 4, KHC (3 ⁇ 4).
  • the precursor of the active component in the step (3) is palladium chloride. , palladium bromide, platinum chloride and ruthenium chloride, palladium nitrate, platinum nitrate, palladium acetate, acetic acid, preferably palladium chloride and palladium acetate.
  • the platinum group metal salts may be used singly or in combination.
  • the precursor of the catalyst auxiliary in the step (3) is one or more of ferric chloride, cobalt bromide, ferric nitrate, nickel nitrate, cobalt acetate, and nickel acetate.
  • the structured crucible catalyst of the present invention is applied to a C.O coupled synthetic oxalate reaction wherein the oxalate is one or both of dimethyl oxalate or diethyl oxalate.
  • the invention provides a method for producing oxalate by CO gas phase coupling using the above-mentioned structured catalyst, characterized in that it comprises the steps of: using a fixed bed reactor, the catalyst bed is composed of a regular structure catalyst supporting a noble metal, and the reaction pressure is 0.1- 2MPa, reaction temperature is 80-20CTC, with ⁇ as carrier gas, CO and vaporized nitrous acid
  • the ester enters the reactor and reacts on the structured catalyst to produce oxalate.
  • the catalyst bed layer is composed of a reforming catalyst of a noble metal.
  • the production method of the method for producing oxalate by CO gas phase coupling using a structured catalyst according to the present invention has a reaction pressure of 0, 1-1.2 MPa and a reaction temperature of 90-150 °C.
  • the nitrite described in the production method of synthesizing oxalate by CO gas phase coupling using a structured catalyst according to the present invention is one or two of methyl nitrite or ethyl nitrite.
  • the invention is compared to known techniques and is characterized in that -
  • the structured catalyst provided by the invention is firstly applied to the CO gas phase coupling oxalate system, which provides a new idea for the development of CO gas phase coupling oxalate catalyst.
  • the alkali treatment method in the preparation method of the regular structure catalyst improves the interaction between the active component and the carrier, and effectively improves the catalytic activity of the CO coupled synthetic oxalate.
  • the structured catalyst of the present invention has a lower internal diffusion resistance than the supported particulate catalyst applied to CO gas phase coupling to oxalate, since the active component of the catalyst is mainly concentrated on the extremely thin coating carrier.
  • the use of a structured catalyst enhances the mass transfer efficiency of the reaction material between the gas-solid phase and reduces the amount of precious metal used (the amount of catalyst precious metal used is much lower than that of the conventional particulate catalyst, saving more than 86%).
  • the catalyst's reactivity is comparable and the cost of the catalyst in oxalate production is greatly reduced.
  • the economics of the CO gas phase coupling oxalate process technology has been improved.
  • the structured catalytic ruthenium of the present invention is advantageous for reducing the pressure drop of the catalyst bed, reducing the energy consumption, and being suitable for a large high diameter, compared with the supported particulate catalyst for CO gas phase coupling to oxalate. Production is carried out under conditions, thereby greatly increasing the oxalate production capacity of a single unit and reducing the process operation cost of oxalate synthesis.
  • the use of the structured catalyst of the present invention for CO coupling synthesis of oxalate has novelty and high economic efficiency, and provides a new process route for synthesizing oxalate by coal or natural gas route, which is helpful to promote Engineering of CO coupled synthetic oxalate technology.
  • Fig. 1 is an external view of a honeycomb ceramic and a structured catalyst after coating and active components, and has a regular parallel pore structure by the visible visible catalyst.
  • Figure 2 is a single pore structure diagram of a structured catalyst.
  • Figure 3 is an electronic scanning electron micrograph of a single-wall structure of a structured catalyst.
  • Figure 4 is an elemental distribution diagram of a single wall cross section of a structured catalyst.
  • Figure 5 shows the stability data of the catalyzed oxalate counters in the CO coupling synthesis before and after the modification of the auxiliaries.
  • a 400-well/inches cordierite ceramic honeycomb carrier ( ⁇ 25 mn x 25 mm) was placed in a muffle furnace at 700 ° C for 2 hours to remove organic impurities, and then a conventional dip coating method was used to load the alumina coating, and the dip coating was as described above.
  • Alumina Kang liquid after drying, microwave drying and weighing, dip coating several times until the alumina loading reaches 20wt.%, then heat up to 1200 ° C in the muffle furnace for 4 hours, then in PdCl 2 - a 3 hydrochloric acid
  • the solution was immersed for 5 minutes, wherein the molar concentrations of PdCl 2 and FeCl 3 were 0.2 M and 0.13 M, respectively, and after drying, the mixture was treated at 3 C for 4 hours at 50 CTC to obtain a Pd content of 1.0 wt.%.
  • Fig. 1 is an external view of a honeycomb ceramic and a structured catalyst after coating and active components, and has a regular parallel pore structure by the visible visible catalyst.
  • Figure 2 is a single pore structure diagram of a structured catalyst.
  • Figure 3 is an electronic scanning electron micrograph of a single-wall structure of a structured catalyst. It can be seen from Figure 3 that the oxide support coating is primarily attached to the outer surface of the honeycomb substrate.
  • Figure 4 is an elemental distribution diagram of a single-wall cross section of a structured catalyst (obtained by EDS scanning from the direction of A to B shown in Figure 3). From the distribution of elements in Figure 4, A1: the aluminum oxide coating is mainly concentrated on the honeycomb base. The outer surface has a thickness of about 15 ⁇ m, and the active component Pd is substantially uniformly distributed in the coating layer, and rarely enters the inside of the honeycomb matrix, exhibiting an active component eggshell type distribution, thereby making the internal diffusion resistance much lower.
  • the prepared catalyst having a volume of 12 ml prepared above was charged into a fixed bed reactor, and after the N 2 displacement system, CO and methyl nitrite were preheated and then entered into the system to react on the structured catalyst to form dimethyl oxalate.
  • the reaction results are shown in Table 1.
  • the oxalate synthesis method is the same as in Example 2, and the reaction results are shown in Fig. 5.
  • Example 4 The procedure was the same as in Example 1 except that the skeleton carrier used a 6:00 hole/square inch cordierite ceramic honeycomb carrier. A catalyst having a Pd content of 1.0 wt.% (grand for alumina coating) and a Pd/Fe atomic ratio of 1.5:1 was obtained, 1.0% Pd-Fe/20%a-Al 2 O 3 /COrdierite. The oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 4 Example 4:
  • Example 1 Except that the ball mill ball milling time was 4.5 hours, the other procedure was the same as in Example 1, to obtain a catalyst of 1.0% Pd-Fe/20% a-Al 2 O 3 /Cordierite (Pd/Fe atom ratio of 1.5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 1 The procedure was the same as in Example 1 except that the ball mill ball milling time was 9 hours, and the catalyst was obtained at 1.0 °/. Pd-Fe/20%a-Al 2 O 3 /Cordierite (M/Fe atomic ratio 1.5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 1 Except for the ball: mill ball milling time was 36 hours, the other procedure was the same as in Example 1, to obtain a catalyst of 1.0% Pd-Fe/20% a-Al2O 3 /Cordierite (Pd/Fe atom ratio of 1.5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 1 Except that the slurry prepared in Example 1 was diluted with water to a ratio of 0.8 times so that the alumina coating loading was 5 wl.% and PdCl 2 and ?
  • the other processes were the same as in Example 1 except that the 6 molar concentrations were 0.2 M and 0.1 M, respectively, and the Pd content was 1.0 wt. /. (relative to the alumina coating), a catalyst having a Pd/Fe atomic ratio of 2; 1 : 1.0% Pd-Fe/5%a-Al 2 O 3 ./Cordierite
  • Example 1 The slurry prepared in Example 1 was diluted with water to 0.8 times and dip coated several times until the alumina coating loading was 10 t.% and the PdCl 2 and FeCl 3 molar concentrations were 0.2 M and 0.1 M, respectively.
  • the other procedure was the same as in Example 1 to obtain a catalyst having a Pd content of 1.0 wt.% (relative to the alumina coating) and a Pd/Fe atomic ratio of 2:1 of 1.0% Pd-Fe/10%a-Al 2 O 3 . /Cordierite (Pd/Fe atomic ratio 2: 1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 9 In addition to increasing the number of times of dip-coating of the ball-milling slurry in Example 1, until the alumina coating loading was 30 wt% and the PdCl 2 and FeCl 3 molar concentrations were 0.2 M and 0.067 M, respectively, The procedure was the same as in Example 1 to obtain a catalyst having a Pd content of 1.0 wt.% (relative to the alumina coating) and a Pd/Fe atomic ratio of 3:1 of 1.0% Pd-Fe/30%a-Al 2 O 3 / Cordierite (Pd/Fe atomic ratio 3: 1). The oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • the 400 ?LZ square inch cordierite ceramic honeycomb carrier (; 25 mm x 25 mm) was placed in a muffle furnace and calcined at 700 ° C for 2 hours to remove organic impurities. Then, the ceramic honeycomb carrier is immersed in an alkaline or acidic silica sol by a conventional dip coating method, and the silica carrier coating is obtained by microwave drying, and the impregnation method is used until the silica loading reaches 20 wt.%, and then in the muffle furnace.
  • the temperature was raised to 900 C for 4 hours, and then the hydrochloric acid solution having a concentration of PdCl 2 and FeCl 3 of 0.2 M and 0.13 M, respectively, was immersed, and after drying for 3 hours at 500 Torr for 4 hours, a Pd content of 1.0 wt.% was obtained (relatively.
  • the catalyst having a Pd/Fe atomic ratio of 1.5:1 was 1.0% Pd-Fe/20% SiO 2 /Cordierite (Pd/Fe atomic ratio 1.5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • the catalyst was prepared in the same manner as in Example 8 except that the titanium sol was used as the carrier-coated precursor.
  • the catalyst was 1.0% Pd-Fe/20% TiO 2 /Cordierite (Pd/Fe atomic ratio 1.5:1). .
  • the catalyst was prepared in the same manner as in Example 8 except that zirconia ball-milling was used as the carrier-coated precursor.
  • the catalyst was 1.0% Pd-Fe/20% ZrO 2 /Cordierite (Pd/Fe atomic ratio 1.5:1).
  • Example 1 The procedure was the same as in Example 1 except that 0.5 g of Mn(N. 3 ) 2 was added to the coating slurry to obtain a catalyst of 1.0% Pd-Fe/2O%Al2O 3 -MnO/Cordierite (Pd/Fe atomic ratio 1.5). : 1 ).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 1 In addition to changing the body before the active ingredient and the molar concentration 13 ⁇ 401 2 11 ⁇ 2 3 0.02M solution and 0.013 M, respectively, they will have to palladium supported in an amount of 0. lwt.%, The same as other procedures of Example 1 to obtain a Pd content of 0. Lwt. (relative to the alumina coating), a catalyst having a Pd/Fe atomic ratio of 1.5:1, 0.1% Pd-Fe/20%a-Al 2 ⁇ 3 ⁇ 4'' Cordierite (Pd/Fe atomic ratio 1.5:1). The oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • the PdCl 2 and FeCl 3 solutions were changed to a molar concentration of 0.4 M and 0.27 M, respectively, so that the palladium loading was 2,0 wt.%.
  • the other procedures were the same as in Example 1, and the Pd content was 2.0 wt%. (relative to the alumina coating), the Pd/Fe atomic ratio is 1.5; 1 catalyst 2.0% Pd-Fe/dA O /Cordierite (PdZFe atomic ratio 1.5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 18 Using the catalyst preparation method of Example 1, by changing the concentrations of PdCl 2 and FeC solutions to 0.2 M and 2 M, respectively, the Pd content was 1,0 w % (relative to the alumina coating), and the Pd/Fe atomic ratio was 0 ⁇ . : catalyst 1 ⁇ : agent 1.0 0 / oPd-Fe / 20 % a-Al 2 03 / Cordieriteo oxalate synthesis of Example 1 the same embodiment, the reaction results shown in Table 1.
  • Example 18 Example 18
  • Example 19 Using the catalyst preparation method of Example 1, by changing the concentrations of the PdCl 2 and : FeCl 3 solutions to 0.2 M and 0.08 M, respectively, a Pd content of 1.0 wt.% (relative to the alumina coating), Pd/Fe atomic ratio was obtained.
  • the synthesis method of 1.0:1 Pd-Fe/20%a-Al2O 3 /Cordierite 0 oxalate of 2.5:1 was the same as that of Example 1, and the reaction results are shown in Table 1.
  • Example 19 The synthesis method of 1.0:1 Pd-Fe/20%a-Al2O 3 /Cordierite 0 oxalate of 2.5:1 was the same as that of Example 1, and the reaction results are shown in Table 1.
  • Example 19 Using the concentrations of the PdCl 2 and : FeCl 3 solutions to 0.2 M and 0.08 M, respectively, a Pd content of 1.0 wt.% (relative to the alumina coating),
  • the active component precursor solution is Pt(N0 3 ) 2 -Ni(N0 3 ) 2 hydrochloric acid solution (the concentrations of R.(N0 3 ) 2 and Ni(NO 3 ) 2 solutions are 0.02M and 0.02M, respectively).
  • the other processes are the same as in the first embodiment.
  • the Pt content is 0. lwt.% (relative to the alumina coating), the Pt'Ni atomic ratio is 1; 1 catalyst 1.0% Pt-Ni/20% oc-Al 2 0 3 /Cordierite (Pt/Ni atom Than 1: 1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 2 The process was the same as in Example 1 except that PdCb-IrCU-l/eClj hydrochloric acid solution (PdCl 2 , IrCl 4 and FeCl 3 concentrations of 0.15 M, 0.03 M and 0.13 M, respectively) was used instead of PdCl 2 .FeCl 3 hydrochloric acid solution. , a catalyst of 0, 8% Pd-0.1% Ir-Fe/20 a-Al 2 O 3 /Cordierite C CPd + Ir) / Fe atomic ratio 1.2: 1 ) was obtained.
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 1 The same as in Example 1, except that after impregnating the PdCl 2 -FeCl 3 hydrochloric acid solution and drying, the concentration is 0.2M. Na 2 C (solution treated for 6 hours, Pd content is U) wt.% (relative to alumina coating), Pd/Fe atomic ratio is 1.5; 1 catalyst 1.0% Pd-Fe/20% a-Al 2 O 3 /Cordierite (Pd/Fe atomic ratio 1.5: 1 ).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Example 21 Except that NaOH solution was used instead of Na 2 .C (3 ⁇ 4 solution for alkali treatment, the other process was the same as in Example 21, and the Pd content was 1.0 wt.% (relative to the alumina coating), and the Pd/Fe atomic ratio was 1.
  • the catalyst of 5:1 was 1.0% Pd-Fe/20%-Al2O 3 /Cordierite (Pd/Fe atomic ratio 1,5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • the catalyst was the same as in Example 1 except that CO was reduced at 200 ° C for 10 hours, and a catalyst having a Pd content of 1.0 wt.% (vs. alumina coating) and a Pd/Fe atomic ratio of 1.5 : 1 was obtained. 1.0% Pd-Fe/20% -Al2O3/Cordierite (Pd/Fe atomic ratio 1.5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • a metal honeycomb support (triangular channel, 400 cpsi, ⁇ 25 mm x 25 ffim) was washed in acetone and ethanol to remove organic matter on the surface of the metal support, followed by washing with deionized water and baking at 800 Torr for 10 hours.
  • the alumina carrier coating was then coated in the alumina ball mill of Example 1 using conventional dip coating and then oven dried. After multiple impregnation, the alumina loading reaches 20%, and then the temperature is raised to 120CTC in the muffle furnace for 4 hours, then the solution of PdCl 2 and FeCl 3 is 0.2M, and after drying, it is reduced by 3 ⁇ 4 at 50CTC.
  • a catalyst having a Pd content of 1.0 wt% (relative to the alumina coating) and a Pd/Fe atomic ratio of 1:1 was 1.0% Pd-Fe/20% a-Al 2 O 3 /Metal monolith.
  • the oxalate synthesis method was the same as in Example 1 except that the metal honeycomb carrier was used, and the reaction results are shown in Table 1. Comparative Example 2
  • Example 1 The procedure was the same as in Example 1 except that the active component was impregnated and dried at 400 °C for 2 hours, and the Pd content was 1.0 wt.% (relative to the alumina coating), and the Pd/Fe atomic ratio was 1. 5:1 of catalyst 1,0% Pd-Fe/20%a-Al 2 (3 ⁇ 4ZCordierite (Pd/Fe atomic ratio 1.5:1).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • the catalyst preparation method was the same as in Example 1, to obtain a catalyst 1G% Pd-Fe/20%a-Al 2 O 3 /Cordierite (Pd/Fe atomic ratio 1.5: 1. ).
  • the oxalate synthesis method was the same as in Example 1, and the reaction results are shown in Table 1.
  • Comparative Example 4 Using a strip of 0t-Al 2 O 3 of ⁇ 2-3 ⁇ , the temperature was raised to 1200 ° C in a muffle furnace for 4 hours to obtain a particulate catalyst carrier, followed by impregnation of PdCl 2 -FeCl 3 hydrochloric acid solution (PdCl 2 and: FeCl 3 solution). The granules having a Pd content of 0.1 wt..% and a Pd/Fe atomic ratio of 1.5 : 1 are obtained. %Pd-Fe/a-Al 2 0 3 .
  • the oxalate synthesis method was the same as in Example 1 except that the particulate catalyst was used, and the reaction results are shown in Table 1.
  • the procedure was the same as in Comparative Example 5 except that the concentrations of the PdCl 2 and FeCl 3 solutions were changed to 0.2 M and 0.13 M, respectively.
  • the oxalate synthesis method was the same as in Example 1 except that the particulate catalyst was used, and the reaction results are shown in Table 1.
  • the feed volume ratio was: N 2 : CO: methyl nitrite 0:40:20, and the rest were the same as in Example 1. See the table for the reaction results.
  • Example 34
  • the structured structure catalyst of the present invention is applied to CO gas phase coupling synthesis oxalate reaction.
  • the inventive structured structured catalyst reaches 450 gDMO/Lh (see Example 13), and exceeds 409 g DMO/Lh of the particulate catalyst. (See Comparative Example 5), showing excellent catalytic performance.
  • the highest space-time yield of oxalate can reach 920 gDMO/Lh.
  • the absolute amount of precious metal supported on the unit volume-regulated catalyst was only 14% by weight based on the absolute amount supported on the particulate catalyst.
  • the precious metal usage of the structured catalyst is saved by more than 86%, the cost of the catalyst and the production cost of the oxalate are greatly reduced, and since the structured catalyst is composed of a plurality of parallel channels arranged neatly, the bed void ratio is large, and the reaction stream is The extremely low resistance loss across the catalyst bed contributes to large-scale industrial applications.
  • Example 14 a, wt% composition ratio % rate, g/I h amount, wt% auxiliary
  • Example 1 16 A1 2 0 3 20 Pd 1 Fe 1.14 1,5 32 347
  • Example 3 16 AI2O3 20 Pd 1 Fe 1.14 1.5
  • Example 4 4.5 AI2O3 20 Pd 1 Fe 1.14 1.5 27 276
  • Example 5 9 A1 2 0 3 20 Pd 1 Fe 1.14 1.5 29 308
  • Example 6 36 AI2O3 20 Pd 1 Fe 1,14 1.5 33 357
  • Example 7 16 AI2O3 5 Pd 1 Fe 0.29 2 28 292
  • Example 8 16 AI2O3 10 Pd 1 Fe 0.57 2 31 324
  • Example 9 16 Al 2 Oj 30 Pd 1 Fe 1.71 3 39 390
  • Example 10 ⁇ Si0 2 20 Pd 1 Fe 1.14 1.5 31 321
  • Example 11 16 Ti0 2 20 Pd 1 Fe 1,14 1.5 2 300
  • Example 12 16 Zr0 2 20 Pd 1 Fe 1.14 1.5 27 285
  • Example 13 16
  • Example 25 0.1 120 40:40:20 1.2 Ethyl nitrite 1 1.14 34 420
  • Example 27 0,6 110 50:30:20 3.6 Methyl nitrite 1 1.14 45 920
  • Example 28 0.1 90 50:30:20 1.5 Methyl nitrite 1 1.14 24 257
  • Example 29 0.1 150 50:30:20 1.5 Methyl nitrite 1 1.14 58 608
  • Example 30 0.1 1 10 20:40:40 1.5 Methyl nitrite 1 1.14 50 530
  • Example 31 0,1 110 40:40:20 1,5 Methyl nitrite 1 1.14 37
  • Example 32 0.1 110 50:40: 10 1.5 Methyl nitrite 1 1, 14 20 215
  • Example 33 0,1 110 75:20:5 1 Methyl nitrite 1 1.14 18 105
  • Example 34 0.1 110 50:30:20

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Description

用于 CO气相偶联合成草酸酯的规整催化剂及其制备方法与应用 技术领域
本发明涉及草酸酯的合成， 特别是涉及一种用于 CO气相偶联合成草酸酯的规整催化 剂及其制备方法， 以及使用该规整催化剂甴 CO气相偶联合成草酸酯的生产方法。 背景技术
针对世界石油资源日益枯竭的现状， 采用煤或天然气合成乙二醇技术， 具有重荽的现 实意义。 同时该技术被普遍认为是原料路线科学、 资源利用合理的一项重大 C1化学技术。 草酸酯作为其中重要的中间产物，它的合成技术是"煤或天然气制乙二醇 "的核心技术之一。 除此之外， 草酸酯坯是重要的有机化工原料， 大量用于精细化工制备各种染料、 医药、 重 要的溶剂、 萃取剂以及各种中间体。
传统的草酸酯生产工艺成本高， 能耗大， 污染严重， 原料利用不合理。 目前较为先进 的合成方法是醇氧化羰基化法，特别是 CO气相催化偶联制草酸酯体系中， 在气相醇氧化羰 基合成过程中引入载氧体亚硝酸酯 （RONO, R为烷烃基）， 使反应在温和条件下进行。 反 应过程生产的一氧化氮， 进一歩与醇、 氧气反应生成亚硝酸酯， 整个工艺形成一个自封闭 循环过程、 无三废排放。 其反应方程式如下- 合成反应： 2RONO f2CO→(COOR)2 2 O
再生反应： 2NO+2ROH+l/202→2RONO+H20
此法具有原料来源广泛、 原子经济性好、 反应条件温和、 消耗能耗少、 过程无污染、 产品选择性高、产品质量好等优点。工艺路线为洁净生产工艺,具有明显的经济效益和社会 效益， 受到国内外普遍的关注和重视， 现阶段各国均处于研究或工业开发阶段。 近年来， 国内外许多学者在催化剂的评选、活性及载体效应、工艺操作条件等方面取得一定的进展， 但由于普遍使用贵金属 Pd为催化剂的活性组分， 催化剂费用昂贵， 增大了草酸酯的生产成 本， 使得该工艺路线的经济性降低。
规整结构的蜂窝催化剂具有规整的平行纵向通道， 压降小， 适于高空速下运行， 具有 反应器体积小、 整体装配、 易于更换、 传质效果好以及负载量低、 活性高等特点， 近几年 其在气固和气液固多相反应中的应用研究受到越来越多的关注。 但是在 CO气相偶联合成 草酸酯方面， 规整结构催化剂的研究尚无文献报道。 发明内容
本发明的一个目的是提供一种用于 CO气相偶联合成草酸酯的规整催化剂, 读规整催 化剂减少了催化剂中贵金属的使用量， 具有催化话性高， 成本低特点。 为煤或天然气路线 合成草酸酯提 t了一条崭新的工艺路线， 有助于大力推动 CO偶联合成草酸酯技术的工程 化。 本发明的另一个目的是提供一种用于 CO气相偶联合成草酸酯的规整催化剂的制备方 法， 该制备方法采用浸涂法负载涂层， 采用碱处理和在氢气或 CO氛围中进行处理， 有效 提髙了 CO偶联合成草酸酯催化剂的催化活性。 同时， 将催化剂活性组分限制在载体涂层 中， 由于涂层极薄因此有效降低了扩散阻力， 提高了反应物料在气固或气液固相之间的传 质效率，增大了反应物料与催化剂的接触面积，使活性组分的催化能力得到大幅度的提高。
本发明的再一个目的是提供一种使用规整催化剂由 CO气相偶联合成草酸酯的生产方 法。 使用规整催化剂代替传统颗粒催化剤由 CO偶联合成草酸酯的生产工艺， 有利于降低 催化剂床层的压力降， 从而有助于进一步提升合成草酸酯单套设备的生产能力。 同时也减 小催化剂在装填和使用过程中因磨损而带来的损耗， 降低催化剂的使用成本。 本发明具有 催化活性高， 成本低， 更换方便快捷等特点， 有利于实观大规模工程化应用。 本发明提供的一种用于 CO气相偶联合成草酸酯的规整结构催化剂是以陶瓷峰窝或金 属蜂窝为骨架载体， 以金属氧化物为载体涂层， 以贵金属 Pt、 Pd、 Ir、 Rh为活性组分， 以 Fe、 Co、 Ni为助剂制成；
具体制备步骤： 将金属的硝酸盐、 氢氧化物或氧化物与稀硝酸混合， 在球磨机球磨制 得用于涂覆载体的球磨胶, 该球磨胶采用浸 ¾¾方式对陶瓷蜂窝或金属蜂窝载体进行载体涂 层负载， 干燥， 在马弗炉中焙烧形成金属氧化物载体涂层， 再置于活性组分和助剂的前躯 体溶液中采用浸渍法进行活性组分和助剂的负载， 干燥后在 ¾或 CO气氛下处理； 或浸渍 活性组分和助剂后干燥并用碱溶液处理， 干燥后在 ¾或 CO气氛：下处理。
本发明所述的金属氧化物涂层组分为 Al2¾、 Si02、 Zr02、 TiG)2、 Fe203、 La203、 CuO、 ZnO、 Cr203、 GaO、 BaO, CaO、 MgO、 MnO中的一种或几种。. 或
本发明所述的金属氧化物涂层组分为 Al2<¾、 Si(¾、 Zr(¾、 Ti02、 Fe2<¾、 La2<¾、 CuO、 ZnO, Cr2<¾、 GaO、 BaO, CaO中的一种或几种。
本发明所述的活性组分为 Pt、 Pd、 Ir、 Rh中的一种或多种。
本发明所述用于 CO气相偶联合成草酸酯的规整结构催化剂的助剂为 Fe、 Co, Ni中 的一种或多种。
本发明所述用于 CO气相偶联合成草酸酯的规整结构的催化剂的助剂还包括 Cu或 Ce。 本发明所述用于 CO气相偶联合成草酸酯的规整结构的催化剂的载体涂层占蜂窝载体 重量的 5-50%，催化剂活性组分占载体涂层重 1：的 0.1-5 %，催化剂助剂占载体涂层重量的 0.03-10 ?。， 活性组分与助剂原子比为 0.01-5。
本发明所述用于 CO气相偶联合成草酸酯的规整结构的催化剤的载体涂层占蜂窝载体 重量的 5-50%，催化剂活性组分占载体涂层重量的 0.1-5 %，催化剂助剂占载体涂层重量的 0.3-10% , 活性组分与助剂原子比为 0.1-5。
本发明所述用于 CO气相偶联合成草酸酯的规整结构的催化剂的载体涂层占蜂窝载体 重量的 5-30% ,催化剂活性组分占载体涂层重量的 0,1-2 % ,催化剂助剂占载体涂层重量的 0.3-6% , 活性组分与助剂原子比为 0.1-3。
本发明提供上述用于 CG)气相偶联合成草酸酯的规整结构催化剂的制备方法， 其特征 在于包括的具体歩骤为；
1)球磨 ¾：胶的制备： 将一种或多种金属的硝酸盐、 氢氧化物或氧化物混合， 加入稀硝 酸， 控制 ΡΗ值为 1-4， 经球磨机球磨 1-48小时后， 制得用于涂覆载体的球磨胶；
2)载体涂层的负载： 使用上述球磨胶采用浸涂方式对陶瓷蜂窝载体或金属蜂窝载体进 行载体涂层负载， 然后干燥； 经过一次或多次浸涂直到负载量达到要求， 最后在马弗炉中 于 900-1300°C条件卞焙烧 1-12小时， 形成载体涂层；
3)活性组分和助剂的负载： 将具有涂层结构的载体置于一种或多种活性组分和助剂的 前躯体溶液中采用浸渍法进行活性组分和助剂的负载， 干燥； 干燥后在 ¾或 CO气氛条件 下处理 1-10小时， 制得所述发明催化剂。
本发明提供的上述规整结构催化剂的制备方法包括的步骤：
( 1 ) 球磨溶胶的制备： 将一种或多种金属的硝酸盐、 氢氧^ ^物或氧化物混合， 加入 浓度为 1-15 wt.. ?'。的稀硝酸， 控制 PH值为 1-4, 经球磨机球磨 3- 20时后， 制得用于涂覆 载体的球磨胶；
( 2) 载体涂层的负载：使用上述球磨胶采用浸涂方式对堇青石陶瓷蜂窝载体或金属 蜂窝载体进行载体涂层负载， 然后在 70-13CTC条件下干燥 2-4 小时， 并在马弗炉中于 900-120(TC条件下焙烧 1-12小时， 形成载体涂层， 涂层负载量为蜂窝载体的 5- 50 wt. %, 为获得高负载量的涂层必须采用多次浸涂方法；
( 3 ) 活性组分的负载：将具有涂层结构的载体置于一种或多种活性组分和助剂的前 躯体溶液中采用浸渍法进行活性组分和助剂的负载， 浸渍时间为 3分钟 -12小时。 浸渍后 的蜂窝催化剂在 70- 13CTC条件下干燥 1-12小时， 最后在 或 CO气氛下于 400-80(TC处 理 l-10h制得所述发明催化剂.。
其中， 上述负载活性组分和助剂之后的载体涂层干燥后再采用浓度为 0.01-2M的碱溶 液处理 0.5-24小时；
所述的碱溶液是 NaOH， KOH, a2C03, K2C03， NaHC<¾， KHC(¾中的一种或多种。 步骤 (3)中活性组分的前躯体是氯化钯、 溴化钯、 氯化铂和氯化锗、 硝酸钯、 硝酸铂、 乙酸钯、 乙酸错， 优选氯化钯和乙酸钯。 铂族金属盐可以单独使用或结合使用。
歩骤 (3)中催化剂助剂的前躯体为三氯化铁、 溴化钴 硝酸铁、 硝酸镍、 乙酸钴、 乙酸 镍中的一种或多种。
本发明所述规整结枸催化剂应用于 C.O偶联合成草酸酯反应中， 其中草酸酯是草酸二 甲酯或草酸二乙酯的一种或两种。
本发明提供采用上述规整催化剂由 CO气相偶联合成草酸酯的生产方法， 其特征在于 它包括的步骤： 采用固定床反应器， 催化剂床层由负载贵金属的规整结构催化剂组成， 在 反应压力为 0.1- 2MPa， 反应温度为 80-20CTC条件下， 以 ^为载气， CO与汽化后的亚硝酸 酯进入反应器在规整催化剂上发生反应生产草酸酯，各物料的体积比为： N2： CO：亚硝酸 酯 = 20-80： 5-60： 10-40, 停留时间为 0,5-10s o
本发明所述采用规整催化剂由 CO气相偶联合成草酸酯的生产方法中催化剂床层由负 载贵金属的规整催化剂组成。
本发明所述采用规整催化剂由 CO 气相偶联合成草酸酯的生产方法的反应压力为 0, 1-1.2MPa, 反应温度为 90- 150 °C。
本发明所述采用规整催化剂由 CO气相偶联合成草酸酯的生产方法的系统进料气.体体 积组成为： N2 ： CO：亚硝酸酯 = 20-8:0： 5-60： 10-40' 停留时间为 1- Os ,
本发明所述采用规整催化剂由 CO气相偶联合成草酸酯的生产方法的系统进料气体体 积组成为： N2 ： CO：亚硝酸酯 = 20-8:0： 5-60： 5-10。
本发明所述采用规整催化剂由 CO气相偶联合成草酸酯的生产方法中所述的亚硝酸酯 是亚硝酸甲酯或亚硝酸乙酯中的一种或两种。 本发明与公知技术相比较， 其特点在于-
1. 本发明提供的规整催化剂首次应用于 CO气相偶联制草酸酯体系中，为 CO气相偶 联制草酸酯催化剂研制提供了一个崭新的思路。
2. 在该规整结构催化剂制备方法中采用碱处理方法改善了活性组分与载体的相互作 用， 有效提高了 CO偶联合成草酸酯的催化活性。
3. 本发明的规整催化剂与应用于 CO气相偶联制草酸酯的负载型颗粒催化剂相比，由 于催化剂活性组分主要集中在极薄的涂层载体上， 因此内扩散阻力大为條低， 使用规整催 化剂提髙了反应物料在气固相之间的传质效率， 减少了贵金属的使用量 （催化剂贵金属的 使用量远远低于常规颗粒催化剂， 节约了 86%以上）， 在与颗粒催化剂反应活性相当的情 况下大幅度降低了催化剂在草酸酯生产中所占成本。 提高了 CO气相偶联制草酸酯工艺技 术的经济性。
4. 本发明的规整催化剤与应用于 CO气相偶联制草酸酯的负载型颗粒催化剂相比，有 利于降低催化剂床层的压力降， 能耗减少， 而且适宜于在较大的高径比条件下进行生产， 从而大幅度提高单套装置的草酸酯生产能力， 降低草酸酯合成的工艺操作成本。
因此， 使用本发明所述规整催化剂用于 CO偶联合成草酸酯具有新颖性和较高的经济 性， 为煤或天然气路线合成草酸酯提供了一条崭新的工艺路线， 有助于大力推动 CO偶联 合成草酸酯技术的工程化。 附图说明
图 1为蜂窝陶瓷与涂覆涂层与活性组分后的规整催化剂的外观图， 由匿可见规整催化 剂具有规整的平行孔道结构。
图 2为规整催化剂的单孔结构图。 图 3为规整催化剂单壁结构的电子扫描电镜图片。
图 4为规整催化剂单壁横截面的元素分布图。
图 5 为助剂改性前后的规整催化剂在 CO偶联合成草酸酯反 ¾中稳定性数据。 具体实施方式
实施例 1 ;
涂层前躯体浆液的准备
称取 12— γ- Al2(¾、 3.5gA100H、 6.5gAl(OH)3及 8.0gAl(NO3)3以及 100ml 10 wt.%的稀 ΗΝ03 '溶液， 经球磨机 （行星式球磨机 XQM-2L, 南京顺驰）在转速为 200转条件下球磨 16小时后制得氧化铝溶胶待用。
催化剂制备
将 400孔 /平方英寸堇青石陶瓷蜂窝载体 (Φ25 mn x25 mm)置于马弗炉中 700°C焙烧 2 小时去除有机物杂质，然后使用常规浸涂法负载氧化铝涂层，浸涂浆液为上述氧化铝康液， 上载后微波干燥并秤重， 浸涂多次直到氧化铝负载量达到 20wt.%后， 在马弗炉中升温至 1200°C保持 4小时， 随后在 PdCl2- a3盐酸溶液中浸渍 5分钟， 其中 PdCl2和 FeCl3的摩 尔浓度分别为 0.2M和 0.13M，干燥后采用 ¾在 50CTC下处理 4小时，得到 Pd含量为 1.0wt.%
(相对于氧化铝涂层）， Pd/Fe原子比为 1.5: 1 的催化剂 1.0%Pd-Fe/20%a- Al203/Cordierite
(Pd/Fe原子比 1.5: 1. )。
图 1为蜂窝陶瓷与涂覆涂层与活性组分后的规整催化剂的外观图， 由匿可见规整催化 剂具有规整的平行孔道结构。 图 2为规整催化剂的单孔结构图。 图 3为规整催化剂单壁结 构的电子扫描电镜图片。 由图 3可见氧化物载体涂层主要附着在蜂窝基体的外表面。 图 4 为规整催化剂单壁横截面的元素分布图（从图 3所示 A到 B的方向进行 EDS扫描得到） ， 从图 4中 A1:元素分布可以看出氧化铝涂层主要集中在蜂窝基体外表面，厚度约为 15微米， 活性组分 Pd则基本均匀分布在涂层中， 极少进入蜂窝基体内部， 呈现活性组分蛋壳型分 布， 从而使内扩散阻力大为條低。
草酸酯合成方法
将上述制备好的体积为 12ml的规整催化剂装入固定床反应器中，采用 N2置换系统后， CO 和亚硝酸甲酯经预热后进入系统在规整催化剂上发生反应生成草酸二甲酯。 反应温度 控制在 lior , 压力控制在 0.1MPa、 迸料体积比为； N2 : CO: 亚硝酸甲酯 =50:30:20、 停 留时间为 1.5s。 反应结果见表 1。
实施例 2:
采用体积为 12nil实施例 1所制备催化剂装入固定床反应器中， 采用 Ν2置换系统后， CO 和亚硝酸甲酯经预热后迸入系统在规整催化剂上发生反应生成草酸二甲酯。 反应温度 控制在 120°C、 压力控制在 0.25MPa、 进料体积比为： N2: CO: 亚硝酸甲酯 =50:30:20、 停 留时间为 7.5s。 反应累积运行 200小时， 反应结果见图 5。 由图可知助剂改性后的规整催 化剂具有更高的稳定性。
比较实施例 1
催化剂制备
除了在浸渍活性组分时， 采甩 0.2M的 PdC 溶液代替 PdCl2禾卩 FeCl3混合溶液外， 其 它催化剂制备过程与实施例 1相同,得到 Pd含量为 1.0wt.% (相对于氧化铝凃层）， 催化剂 1.0%Pd /20%a-Al2O3/Cordierite。
草酸酯合成方法同实施例 2， 反应结果见图 5.
实施例 3:
除了骨架载体采用 6:00孔 /平方英寸堇青石陶瓷蜂窝载体， 其它过程与实施例 1相同。 得到 Pd含量为 1.0wt.% (祖对于氧化铝涂层）， Pd/Fe 原子比为 1.5 : 1 的催化剂 1.0%Pd-Fe/20%a-Al2O3/COrdierite。 草酸酯合成方法与实施例 1相同， 反应结果见表 1。 实施例 4:
除了球磨机球磨时间为 4.5 小时， 其它过程与实施例 1 相同， 得到催化剂 1.0%Pd-Fe/20%a-Al2O3/Cordierite (Pd/Fe原子比 1.5: 1 )。草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 5:
除了球磨机球磨时间为 9 小时， 其它过程与实施例 1 相同， 得到催化剂 1.0°/。Pd-Fe/20%a-Al2O3/Cordierite (M/Fe原子比 1.5: 1 )。草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 6:
除了球：磨机球磨时间为 36 小时，其它过程与实施例 1 相同， 得到催化剂 1.0%Pd-Fe/20%a-Al2O3/Cordierite (Pd/Fe原子比 1.5: 1)。 草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 7:
除了将实施例 1所制备桨液加水稀释为 0.8倍，以使氧化铝涂层负载量为 5wl.%且 PdCl2 和？6 3摩尔浓度分别为 0.2M和 0.1M外， 其它过程与实施例 1相同,得到 Pd含量为 1.0 wt。/。（相对于氧化铝涂层）， Pd/Fe原子比为 2; 1的催化剂: 1.0%Pd-Fe/5%a-Al2O3./Cordierite
(Pd/Fe原子比 2: 1 )。 草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 8:
除了将实施例 1所制备浆液加水稀释为 0.8倍并浸涂多次， 直到使氧化铝涂层负载量 为 10 t.% 且 PdCl2和 FeCl3摩尔浓度分别为 0.2M和 0.1M夕卜， 其它过程与实施例 1相同, 得到 Pd 含量为 1.0wt.% (相对于氧化铝涂层）， Pd/Fe 原子比为 2 : 1 的催化剂 1.0%Pd-Fe/10%a-Al2O3/Cordierite (Pd/Fe原子比 2: 1 )。 草酸酯合成方法与实施例 1相同， 反应结果见表 1。 实施例 9 - 除了将实施例 1中浸涂球磨浆料的次薮增加, 直到使氧化铝涂层负载量为 30wt% 且 PdCl2和 FeCl3摩尔浓度分别为 0.2M和 0.067M夕卜， 其它过程与实施例 1相同，得到 Pd含量 为 1.0wt.% ( 相对于氧化铝涂层 ） ， Pd/Fe 原 子 比为 3 ： 1 的催化剂 1.0%Pd-Fe/30%a-Al2O3/Cordierite ( Pd/Fe原子比 3: 1 )。 草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 10 :
将 400 ?LZ平方英寸堇青石陶瓷蜂窝载体 (； Φ25 mmx25 mm)置于马弗炉中 700°C焙烧 2 小时去除有机物杂质。 然后使用常规浸涂法在碱性或酸性硅溶胶中浸泡陶瓷蜂窝载体， 微 波干燥后得到氧化硅载体涂层， 采用多次浸渍手段直至氧化硅负载量达到 20wt. %后，在马 弗炉中升温至 900 C保持 4小时， 随后浸渍 PdCl2和 FeCl3浓度分别为 0.2M和 0.13M的盐 酸溶液， 千燥后采用 ¾在 500 Γ下处理 4小时， 得到 Pd含量为 1.0wt.% (相对于氧化铝涂 层）， Pd/Fe原子比为 1.5： 1的催化剂 1.0%Pd-Fe/20%SiO2/Cordierite ( Pd/Fe原子比 1.5： 1 )。 草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 1 1
前躯体浆液的准备
称取 I5.0g偏钛酸， 加入盐酸 10ml 和硝酸 10ml， 球磨 16小时后制得氧化钛溶胶待 用。
催化剂制备
除采用钛溶胶为载体涂层前躯体外， 催化剂制备方法与实施例 8 同， 得到催化剂 1.0%Pd-Fe/20%TiO2/Cordierite ( Pd/Fe原子比 1.5： 1 )。.
草酸酯合成
草酸酯合成方法同实施例 1， 反应结果见表 1。
实施例 12- 涂层前躯体桨液的准备
称取 16.5gZr(OH)4， 15.0g Zr(NO3)4'5¾O, 3.0gZrO2， 加入 50ml HNO3， 球磨 16 小时后 制得氧化锆球磨胶待用。
催化剂制备
除采用氧化锆球磨胶为载体涂层前躯体外， 催化剂制备方法与实施例 8同， 得到催化 剂 1.0%Pd-Fe/20%ZrO2/Cordierite (Pd/Fe原子比 1.5 : 1 )。
草酸酯合成
草酸酯合成方法同实施例 1， 反应结果见表 1。
实施例 13 :
除了在涂层浆料中加入 l .:2gM.g(N03)2外， 其他过程与实施例 1 相同， 得到催化剂 1.0%Pd-Fe/20%Al2O3-MgO/Cordierite ( Pd/Fe原子比 1.5 : 1 )。 草酸酯合成方法与实施例 1 相同， 反应结果见表 1。
实施例 14;
除了在涂层浆料中加入 0.5g Mn(N。3)2外, 其他过程与实施例 1 相同， 得到催化剂 1.0%Pd-Fe/2O%Al2O3-MnO/Cordierite (Pd/Fe原子比 1.5： 1 )。 草酸酯合成方法与实施例 1 相同， 反应结果见表 1。
实施例 15:
除了改变活性组分前躯体 1¾012和1½ 3溶液的摩尔浓度分别为 0.02M和 0.013M， 便得钯 负载量为 0. lwt.%, 其它过程与实施例 1相同,得到 Pd含量为 0. lwt. (相对于氧化铝涂层)， Pd/Fe原子比为 1.5: 1的催化剂 0.1%Pd-Fe/20%a-Al2<¾''Cordierite ( Pd/Fe原子比 1.5: 1 )。 草 酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 16:
除了改变活性组分前躯体 PdCl2和 FeCl3溶液的摩尔浓度分别为 0.4M和 0.27M, 使得 钯负载量为 2,0wt.%, 其它过程与实施例 1相同,得到 Pd含量为 2.0wt% (相对于氧化铝涂 层）， Pd/Fe原子比为 1.5； 1的催化剂 2.0%Pd- Fe/d-A O /Cordierite (PdZFe原子比 1.5: 1 )。 草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 17:
采用实施例 1的催化剂制备方法， 通过改变 PdCl2和 FeC 溶液的浓度分别为 0.2M和 2M , 得到 Pd含量为 l ,0w % (相对于氧化铝涂层)， Pd/Fe 原子比为 0丄： 1 的催^：剂 1.00/oPd-Fe/20%a-Al203/Cordieriteo 草酸酯合成方法与实施例 1相同， 反应结果见表 1。 实施例 18：
采用实施例 1的催化剂制备方法， 通过改变 PdCl2和： FeCl3溶液的浓度分别为 0.2M和 0.08M , 得到 Pd含量为 1.0wt.% (相对于氧化铝涂层）， Pd/Fe原子比为 2.5: 1 的催化剂 1.0%Pd-Fe/20%a-Al2O3/Cordierite 0 草酸酯合成方法与实施例 1相同， 反应结果见表 1。 实施例 19:
除了活性组分前躯体溶液为 Pt(N03)2-Ni(N03)2盐酸溶液外（R.(N03)2和 Ni(NO3)2溶液 的浓度分别为 0.02M和 0.02M) , 其它过程与实施例 1相同。 得到 Pt含量为 0. lwt.% (相 对于氧化铝涂层）， Pt'Ni原子比为 1 ; 1的催化剂 1.0%Pt-Ni/20%oc-Al203/Cordierite (Pt/Ni 原子比 1 : 1 )。 草酸酯合成方法与实施例 1 ,相同， 反应结果见表 1。
实施例 20
除了采用 PdCb-IrCU-l/eClj盐酸溶液（ PdCl2、IrCl4和 FeCl3的浓度分别为 0.15M、0.03M 和 0.13M ) 代替 PdCl2.FeCl3盐酸溶液外, 其它过程与实施例 1 相同，得到催化剂 0,8%Pd-0.1%Ir-Fe/20 a-Al2O3/Cordierite C CPd+Ir) /Fe原子比 1.2: 1 )。 草酸酯合成方法与 实施例 1相同， 反应结果见表 1。
实施例 21
其^!歩骤同实施例 1， 只是在浸渍 PdCl2-FeCl3盐酸溶液并干燥后， 再用浓度为 0.2M 的 Na2C( 溶液处理 6小时， 得到 Pd含量为 U)wt.% (相对于氧化铝涂层）， Pd/Fe原子比 为 1.5; 1的催化剂 1.0%Pd-Fe/20%a-Al2O3/Cordierite ( Pd/Fe原子比 1.5： 1 )。. 草酸酯合成 方法与实施例 1相同， 反应结果见表 1。
实施例 22
除了采用 NaOH溶液代替 Na2.C(¾溶液进行碱处理夕卜， 其他过程同实施例 21相同， 得 到 Pd 含量为 1.0wt.% (相对于氧化铝涂层）， Pd/Fe 原子比为 1,5 : 1 的催化剂 1.0%Pd-Fe/20% -Al2O3/Cordierite ( Pd/Fe原子比 1,5: 1 )。草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 23
除了采用 CO在 200°C条件下还原 10小时外， 其他过程同实施例 1相同， 得到 Pd含 量为 1.0wt.% (相对于氧化铝涂层） ， Pd/Fe 原子比为 1.5 ： 1 的催化剂 1.0%Pd-Fe/20% -Al2O3/Cordierite ( Pd/Fe原子比 1.5: 1 )。草酸酯合成方法与实施例 1相同， 反应结果见表 1。
实施例 24 :
将金属蜂窝载体 (三角形孔道， 400cpsi , Φ25 mmx25 ffim)在丙酮和乙醇溶液中洗錄， 去除金属载体表面的有机物， 之后使用去离子水洗绦， 在 800Ό焙烧 10小时。然后使用常 规浸涂法在实施例 1所述氧化铝球磨胶中涂覆氧化铝载体涂层， 然后烘箱干燥。 经过多次 浸渍，氧化铝负载量达到 20 ,%后，在马弗炉中升温至 120CTC保持 4小时， 随后浸渍 PdCl2 和 FeCl3浓度均为 0.2M的溶液， 干燥后采用 ¾在 50CTC下还原 4小时， 得到 Pd含量为 1.0wt% (相对于氧化铝涂层）， Pd/Fe原子比为 1： 1的催化剂 1.0%Pd-Fe/20%a-Al2O3/Metal monolith。 除采用该金属蜂窝载体外， 草酸酯合成方法与实施例 1相同， 反应结果见表 1。 比较实施例 2
除了在浸渍活性组分并干燥后在 400度条件下焙烧 2小时， 其它过程与实施例 1相同， 得到 Pd 含量为 1.0wt.% (相对于氧化铝涂层）， Pd/Fe 原子比为 1,5 : 1 的催化剂 l,0%Pd-Fe/20%a-Al2(¾ZCordierite ( Pd/Fe原子比 1.5: 1 )。草酸酯合成方法与实施例 1相同， 反应结果见表 1。
比较实施例 3
涂层前躯体浆液的准备
使用 200 g γ-Α12<¾粉末为原料， 配置 20%γ-Α12Ο3悬浊液， 用稀 HN03调 ρΗ=5， 搅拌 24小时， 制得氧化铝溶胶待用。
催化剂制备
除采用本实施例所制备的氧化铝溶胶外， 催化剂制备方法与实施例 1同， 得到催化剂 l.G%Pd-Fe/20%a-Al2O3/Cordierite (Pd/Fe原子比 1.5 : 1. )。
草酸酯合成方法与实施例 1相同， 反应结果见表 1。
比较实施例 4: 使用 Φ2-3ηιιη的条状 0t-Al2O3， 在马弗炉中升温至 1200°C保持 4小时后得到颗粒催化 剂载体，随后浸渍 PdCl2-FeCl3盐酸溶液 (PdCl2和： FeCl3溶液的浓度分别为 0.02M和 0.013M)， 千燥后采用 ¾在 500°C下还原 4小时， 得到 Pd含量为 0.1wt..%、 Pd/Fe原子比为 1.5 : 1的 颗粒催化剂 0. l%Pd-Fe/a-Al203。
除采用该颗粒催化剂外， 草酸酯合成方法与实施例 1相同， 反应结果见表 1。
比较实施例 5 :
除了改变 PdCl2和 FeCl3溶液的浓度分别为 0.2M和 0.13M, 其它过程与比较实施例 5 相同。 得到 Pd含量为 1.0wt.% (相对于氧化铝载体）， Pd/Fe 原子比为 1.5 : 1 的催化剂 1.0%Pd-Fe/a-Al2O3。 除采用该颗粒催化剂外， 草酸酯合成方法与实施例 1相同， 反应结果 见表 1。
实施例 25:
采用实施例 1制备的催化剂， 应用于 CO气相偶联合成草酸二乙酯反应， 在反应温度 120 、 压力 0.1MPa、 停留时间为 1.2s、 各物料体积比为 N2 : CO: C2H50NO= 40:40:20、 催化剂用量为 12mL条件下进行反应。 反应结果见表 2。
实施例 26 :
采用实施例 1制备的催化剂， 应用于 CO气相偶联合成草酸二甲酯反应， 在反应温度 13(TC、 压力 0.3MPa、 停留时间为 3s、 各物料体积比为 N2 : CO: CH3ONO= 40:40:20、 催 化剂用量为 48ml条件下进行反应。 反应结果见表 2。
实施例 27:
除反应压力控制在 0.6 MPa， 停留时间为 3,6外， 其余同实施例 1， 反应结果见表 2fi 实施例 28:
除反应温度控制在 90 C外， 其余同实施例 1， 反应结果见表 2。
实施例 29:
除反应压力控制在 150 V外， 其余同实施例 1， 反应结果见表 2。
实施例 30:
除进料体积比为： N2: CO: 亚硝酸甲酯 =20:40:40外， 其余同实施例 1， 反应结果见表
2。
实施例 31 :
除进料体积比为： N2: CO: 亚硝酸甲酯 0:40:20夕卜， 其余同实施例 1。 反应结果见表
2。
实施例 32 :
除进料体积比为： N2: CO: 亚硝酸甲酯 =50:40: 10夕卜， 其余同实施例 1， 反应结果见表
2 ,
实施例 33 :
除进料体积比为： N2: CO:亚硝酸甲酯 =70:25:5外，其余同实施例 1， 反应结果见表 2。 实施例 34:
除停留时间为 Is外， 其佘同实施例 1， 反应结果见表 2。
本发明规整结构催化剂应用于 CO气相偶联合成草酸酯反应， 与负载型颗粒催化剂相 比可知， 所发明使用规整结构催化剂达到 450gDMO/L.h (见实施例 13 )， 超过颗粒催化剂 的 409gDMO/L.h (见比较实施例 5 )， 表现出极佳的催化性能。 通过反应工艺的调变， 草酸 酯最高时空收率能够达到 920 gDMO/L.h。此外，单位体积规整催化剂上贵金属担载绝对量 仅是颗粒催化剂上担载绝对量的 14wt%。可见规整催化剂的贵金属使用量节约了 86%以上， 大幅度降低了催化剂的成本以及草酸酯的生产成本， 并且由于该规整催化剂是由许多平行 通道整齐排列组成， 床层空隙率大， 反应物流逋过催化剂床层的阻力损失极低， 有助于实 现大规模的工业化应用。
表 1. 催化剂在 CO气相偶联合成草酸酯反应中的催化性能 球磨 活性组 活性
涂层载 活性 CO转 空时 催化剂 时间， 涂层组分 分负载 助剂 gPd/L组分 /
a, wt%组分 化率 ％率， g/I h 量, wt% 助剂 实施例 1 16 A1203 20 Pd 1 Fe 1.14 1,5 32 347 实施例 3 16 AI2O3 20 Pd 1 Fe 1.14 1.5 32 339 实施例 4 4.5 AI2O3 20 Pd 1 Fe 1.14 1.5 27 276 实施例 5 9 A1203 20 Pd 1 Fe 1.14 1.5 29 308 实施例 6 36 AI2O3 20 Pd 1 Fe 1,14 1.5 33 357 实施例 7 16 AI2O3 5 Pd 1 Fe 0.29 2 28 292 实施例 8 16 AI2O3 10 Pd 1 Fe 0.57 2 31 324 实施例 9 16 Al2Oj 30 Pd 1 Fe 1.71 3 39 390 实施例 10 ― Si02 20 Pd 1 Fe 1.14 1.5 31 321 实施例 11 16 Ti02 20 Pd 1 Fe 1,14 1.5 2 300 实施例 12 16 Zr02 20 Pd 1 Fe 1.14 1.5 27 285 实施例 13 16 A]203.MgO 20 Pd 1 Fe 1.14 1.5 42 450 实施例 14 16 AI2O3.M11O 20 Pd 1 Fe 1.14 1.5 34 367 实施例 15 16 AI2O3 20 Pd 0.1 Fe 0.11 1.5 16 176 实施例 16 16 AI2O3 20 Pd 2 Fe 2.28 1.5 34 361 实施例 17 16 A1203 20 Pd 1 Fe 1.14 0.1 28 310 实施例 18 16 AI2O3 20 Pd 1 Fe 1.14 2.5 33 332 实施例 19 16 A1203 20 Pt 1 Ni. ― 1 29 301 实施例 20 16 AI2O3 20 Pd-Ir 0.9 Fe 1.2 29 301 实施例 21 16 A1203 20 Pd 1 Fe 1.14 1.5 35 385 实施例 1 16 AI2O3 20 Pd 1 Fe 1.14 1.5 34 370 实施例 23 16 M203 20 Pd 1 Fe 1,14 1.5 33 355 实施例 24 16 AI2O3 20 Pd 1 Fe 1.14 1 32 336 比较实施例 2 16 AI2O3 20 Pd 1 Fe 1,14 1.5 28 300 比较实施例 3 Al2Oj 20 Pd 1 Fe 1.14 1.5 19 220 比较实施例 4 ― ― - Pd 0.1 Fe 0.82 1.5 17 190 比较实施例 5 ― Pd 1 Fe 8.17 1.5 36 409 2. 催化剂在 CO气相偶联合成草酸酯反应中的催化性能 : 反应 N2:CO:亚
反应温 停菌时 Pd负载 CO转化 空时收 催化剂 压力， 硝酸酯 亚硝酸酯 gPd/L
度， 间， s 量, wt% 率 % 率,. g/L.h MPa (v/v/v)
实施例 25 0.1 120 40:40:20 1.2 亚硝酸乙酯 1 1.14 34 420 实施例 26 0.3 130 40:40:20 3 亚硝酸甲酯 1 1.14 38 470 实施例 27 0,6 110 50:30:20 3.6 亚硝酸甲酯 1 1.14 45 920 实施例 28 0.1 90 50:30:20 1.5 亚硝酸甲酯 1 1.14 24 257 实施例 29 0.1 150 50:30:20 1.5 亚硝酸甲酯 1 1.14 58 608 实施例 30 0.1 1 10 20:40:40 1.5 亚硝酸甲酯 1 1.14 50 530 实施例 31 0,1 110 40:40:20 1,5 亚硝酸甲酯 1 1.14 37 406 实施例 32 0.1 110 50:40: 10 1.5 亚硝酸甲酯 1 1, 14 20 215 实施例 33 0,1 110 75:20:5 1 亚硝酸甲酯 1 1.14 18 105 实施例 34 0.1 110 50:30:20 1 亚硝酸甲酯 1 1.14 22 355

Claims

权利要求书
1、 一种用于 CO气相偶联合成草酸酯的规整结构催化剂， 其特征在于它是以陶瓷蜂窝 或金属蜂窝为骨架载体， 以金属氧化物为载体涂层， 以贵金属 Pt、 Pd、 Ir、 R 为活性组分， 以 Fe、 Co、 Ni为助剂制成；
具体制备歩骤： 将金属的硝酸盐、 氢氧化物或氧化物与稀硝酸混合， 在球磨机球磨制 得用于涂覆载体的球磨胶， 该球磨胶采用浸涂方式对陶瓷蜂窝或金属蜂窝载体进行载体涂 层负载， 干燥， 在马弗炉中焙烧形成金属氧化物载体涂层， 再置于活性组分和助剂的前躯 体溶液中采用浸渍法进行活性组分和助剂的负载， 千燥后在 H2或 CO气氛下处理；或浸渍 活性组分和助剂后干燥并用碱溶液处理， 干燥后在 ¾或 CO气氛下处理。
2、 按照权利要求 1 所述的规整结构催化剂， 其特征在于所述的金属氧化物徐层组分 是 Al2(¾、 Si(¾、 Ζι·(¾、 Ti〇2、 Fe2(¾、 La2(¾、 CuO, ZnO、 Cr203、 GaO、 BaO CaO, MgC MnO中的一种或几种。
3、 按照权利要求 1 所述的规整结构催化剂， 其特征在于所述的金属氧化物涂层组分 为 A1203、 SiO'2、 Zr02、 Ti02、 Fe203、 La203、 CuO、 ZnO、 Cr203、 GaO、 BaO、 CaO中的 一种或几种。
4、按照权利要求 1所述的规整结构催化剂， 其特征在于所述的活性组分为 Pt、 Pd、 Ir、 Rh中的一种或多种。
5、 按照权利要求 1所述的规整结构催化剂， 其特征在于所述的助剂为 Fe、 Co, Ni中 的一种或多种。
6、 按照权利要求 1所述的规整结构催化剂， 其特征在于所述的催化剂助剂还包括 Cu 或 Ce fi
7、按照 ¾ί利要求 1所述的规整结构催化剂， 其特征在于所述的 CO气相偶联合成草酸 酯的规整结构的催化剂的载体涂层占蜂窝载体重量的 5-50%， 催化剂活性组分占载体涂层 重量的 0.1-5%，催化剂助剂占载体涂层重量的 0.03-10% ,活性组分与助剂原子比为 0.01-5。
8、按照权利要求 1所述的规整结构催化剂， 其特征在于所述的用于 CO气相偶联合成 草酸酯的规整结构的催化剤的载体涂层占峰窝载体重量的 5-50 %， 催化剂活性组分占载体 涂层重量的 0.1-5 % , 催化剂助剂占载体涂层童量的 0.3-10% , 活性组分与助剂原子比为 0.1-5。
9、按照权利要求 1所述的规整结构催化剂， 其特征在于所述用于 CO气相偶联合成草 酸酯的规整结构的催化剂的载体涂层占蜂窝载体重量的 5-30%， 催化剂活性组分占载体涂 层重量的 0.1-2%，催化剂助剂占载体涂层重量的 0.3-6% ,活性组分与助剂原子比为 0.1-3。
10、 一种权利要求 1所述的用于 CO气相偶联合成草酸酯的规整结构催化剂的制备方 法， 其特征在于包括的步骤为-
1)球磨溶胶的制备： 将一种或多种金属的硝酸盐、 氢氧 物或氧化物混合， 加入稀硝 酸， 控制 PH值为 1-4， 经球磨机球磨 1-48小时后， 制得用于涂覆载体的球磨胶；
2)载体涂层的负载： 使用上述球磨胶采用浸涂方式对陶瓷蜂窝载体或金属蜂窝载体进 行载体涂层负载，然后千燥；经过一次或多次浸涂直到负载量达到要求，最后于 900-1300Ό 条件下焙烧 1-12小时， 形成载体涂层；
3)活性组分和助剂的负载： 将具有涂层结构的载体置于一种或多种话性组分和助剂的 前躯体溶液中采用浸渍法进行活性组分和助剂的负载， 干燥； 干燥后在 ¾或 CO气氛条件 下处理 1-10小时， 制得所述发明催化剂。
11、 一种权利要求 1所述的用于 CO气相偶联合成草酸酯的规整结构催化剂的制备方 法， 其特征在于包括的歩骤：
1 ) 球磨溶胶的制备： 将一种或多种金属的硝酸盐、 氢氧化物或氧化物混合， 加入浓 度为 1-15 wt. %的稀硝酸， 控制 PH值为 1-4， 经球磨机球磨 3-20时后， 制得用于涂覆载 体的球磨胶;
2) 载体涂层的负载： 使用上述球磨胶采用浸涂方式对堇青石陶瓷蜂窝载体或金属蜂 窝载体进行载体涂层负载, 然后在 7()-13(TC条件下干燥 2-4 小时， 并在马弗炉中于 900- 条件下焙烧 1-- 12小时， 形成载体涂层， 涂层负载量为蜂窝载体的 5-- 50 wt. %, 为获得高负载量的涂层必须采用多次浸涂方法；
3) 活性组分的负载： 将具有涂层结构的载体置于一种或多种活性组分和助剂的前躯 体溶液中采用浸渍法进行活性组分和助剂的负载， 浸渍时间为 3分钟 -12小时， 浸渍后的 蜂窝催化剂在 70-13CTC条件下干燥 1-12小时， 最后在 H2或 CO气氛下于 400-80(TC条件 下处理 l-10h制得所述发明催化剂。.
12、 按照权利要求 10或 11所述的方法， 其特征在于所述的负载活性组分和助剂之后 的载体涂层干燥后再采用浓度为 0.01-2M的碱溶液处理 0.5-24小时。
13、 按照权利要求 2 所述的方法， 其特征在于所述的碱溶液是 Na2C03， K2C03， alICO,， KHC03， NaOH， KOH中的一种或多种。
14、 按照权利要求 10或 11所述的方法， 其特征在于所述的活性组分的前躯体是氯化 钯、 溴化钯、 氯化铂和氯化铑、 硝酸钯、 硝酸铂、 乙酸钯、 乙酸铑， 优选氯化钯和乙酸钯； 铂族金属盐可以单独使用或结合使用。
15、 按照权利要求—10或 11所述的方法， 其特征在于所述的催化剂助剂的前躯体为三 氯化铁、： 溴化钴、 硝酸铁、 硝酸镍、： 磷酸铁、 磷酸钴或乙酸钴 乙酸镍中的一种或多种。
16、 一种权利要求 1所述的规整结构催化剂由 CO气相偶联合成草酸酯的生产方法， 其特征在于它包括的步骤： 采用固定床反应器， 催化剂床层由负载贵金属的规整结构催化 剂组成， 在反应压力为 0.1-2MPa， 反应温度为 80- 200°C条件下， 以 N2为载气， CO与汽化 后的亚硝酸酯迸入反应器在规整催化剂上发生反应生产草酸酯， 各物料的体积比为： N2： CO：亚硝酸酯 = 20-80： 5-60： 10-40, 停留时间为 O.S-lOs ^
17、按照 利要求 16所述的生产方法， 其特征在于所述的反应压力为 0.1-1.2MPa， 反 应温度为 90-150°C。
18、 按照权利要求 16所¾的生产方法， 其特征在于所述的系统进^ ·气体体积组成为： N2： CO：亚硝酸酯 = 20-80： 5-60： 10-40, 停留时间为 l-10s：。
19、 按照权利要求 16所述的生产方法， 其特征在于所述的系统进料气体体积组成为- N2： CO：亚硝酸酯 = 20-80： 5-60； 5-10。
20、 按照权利要求 16所述的生产方法， 其特征在于所述的草酸酯是草酸二甲酯或草 酸二乙酯的一种或两种。
21、 按照权利要求 16 所述的生产方法， 其特征在于所述的亚硝酸酯是亚硝酸甲酯或 亚硝酸乙酯中的一种或两种。
PCT/CN2011/075018 2010-06-04 2011-05-31 用于co气相偶联合成草酸酯的规整催化剂及其制备方法与应用 Ceased WO2011150834A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110479287A (zh) * 2019-09-12 2019-11-22 西南石油大学 一种用于合成碳酸二甲酯的整体式催化剂及其制备方法、应用方法
WO2022005676A1 (en) * 2020-06-30 2022-01-06 Dow Technology Investments Llc Processes for reducing the rate of pressure drop increase in a vessel

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105435783B (zh) * 2014-08-27 2018-02-13 中国石油化工股份有限公司 Co气相偶联合成草酸酯的催化剂
CN107335447B (zh) * 2017-06-15 2020-10-27 华南理工大学 一种用于净化挥发性有机物的催化剂及其制备方法
CN111185192A (zh) * 2018-11-15 2020-05-22 河南城建学院 一种用于草酸二甲酯合成的催化剂载体和催化剂
CN111604059A (zh) * 2019-02-22 2020-09-01 上海诺哈尔化工技术有限公司 一种用于草酸酯合成的催化剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101138722A (zh) * 2007-10-10 2008-03-12 天津大学 Co低压气相合成草酸酯的催化剂及其制备方法
CN101851160A (zh) * 2010-06-04 2010-10-06 天津大学 使用规整催化剂由co气相偶联合成草酸酯的生产方法
CN101850273A (zh) * 2010-06-04 2010-10-06 天津大学 由co气相偶联合成草酸酯的规整催化剂及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5980630A (ja) * 1982-11-01 1984-05-10 Ube Ind Ltd シユウ酸ジエステルの製法
IT1097268B (it) * 1978-06-23 1985-08-31 Montedison Spa Processo per la preparazione di esteri dell'acido ossalico
DE2946685C2 (de) * 1979-11-20 1985-06-20 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung eines mit katalyseförderndem Metaloxid beschichteten, in einem Metallmantel angeordneten Verbundkörpers
US4487958A (en) * 1982-09-30 1984-12-11 Union Carbide Corporation Process for preparing a diester of oxalic acid
JPH06145113A (ja) * 1992-11-10 1994-05-24 Daicel Chem Ind Ltd 炭酸ジエステルの製造法
JP2812418B2 (ja) * 1993-05-21 1998-10-22 宇部興産株式会社 エステル化合物の製造法
JP3804813B2 (ja) * 1996-04-16 2006-08-02 宇部興産株式会社 シュウ酸ジエステルの製造法
JP2002273175A (ja) * 2001-03-14 2002-09-24 Toyota Motor Corp 排気ガス浄化装置の製造方法
JP2009165904A (ja) * 2008-01-10 2009-07-30 Honda Motor Co Ltd 排ガス浄化装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101138722A (zh) * 2007-10-10 2008-03-12 天津大学 Co低压气相合成草酸酯的催化剂及其制备方法
CN101851160A (zh) * 2010-06-04 2010-10-06 天津大学 使用规整催化剂由co气相偶联合成草酸酯的生产方法
CN101850273A (zh) * 2010-06-04 2010-10-06 天津大学 由co气相偶联合成草酸酯的规整催化剂及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110479287A (zh) * 2019-09-12 2019-11-22 西南石油大学 一种用于合成碳酸二甲酯的整体式催化剂及其制备方法、应用方法
WO2022005676A1 (en) * 2020-06-30 2022-01-06 Dow Technology Investments Llc Processes for reducing the rate of pressure drop increase in a vessel

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