WO2012159510A1 - Catalyseur de synthèse d'oxalate par une réaction de couplage de co et procédé de fabrication dudit catalyseur - Google Patents

Catalyseur de synthèse d'oxalate par une réaction de couplage de co et procédé de fabrication dudit catalyseur Download PDF

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Publication number
WO2012159510A1
WO2012159510A1 PCT/CN2012/074052 CN2012074052W WO2012159510A1 WO 2012159510 A1 WO2012159510 A1 WO 2012159510A1 CN 2012074052 W CN2012074052 W CN 2012074052W WO 2012159510 A1 WO2012159510 A1 WO 2012159510A1
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WIPO (PCT)
Prior art keywords
catalyst
coating
coupling reaction
wire mesh
active component
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Ceased
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PCT/CN2012/074052
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English (en)
Chinese (zh)
Inventor
计扬
骆念军
毛彦鹏
张博
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Pujing Chemical Industry Co Ltd
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Pujing Chemical Industry SHA Co Ltd
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Priority to JP2014510647A priority Critical patent/JP2014518760A/ja
Publication of WO2012159510A1 publication Critical patent/WO2012159510A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals

Definitions

  • the present invention relates to a catalyst in the field of organic synthesis, and more particularly to a catalyst for synthesizing oxalate by CO coupling reaction and a preparation method thereof. Background technique
  • Oxalate is an important chemical raw material.
  • a variety of chemicals such as oxalic acid, ethylene glycol, and oxalic acid amide can be obtained by using oxalate as a raw material.
  • An object of the present invention is to provide a catalyst for synthesizing oxalate for CO coupling reaction with high activity, good stability and low cost, and a preparation method thereof, in order to overcome the defects of the prior art described above.
  • a catalyst for synthesizing oxalate by CO coupling reaction characterized in that the catalyst is based on a wire mesh, and the surface of the wire mesh is coated with a layer of carrier.
  • the coating, the surface of the carrier coating is loaded with active ingredients and auxiliaries.
  • the wire mesh material is an alloy steel capable of withstanding a temperature exceeding 1000 ° C, and the wire mesh has a pore diameter ranging from 5 mesh to 100 mesh.
  • the carrier coating consists of one or more of alumina, silica, and titania.
  • the carrier coating may be one layer or multiple layers.
  • the mass of the carrier coating is the mass of the entire catalyst. 1% to 55%.
  • the active component is Pd, and the active component Pd accounts for 0.1%-10% of the total catalyst; the auxiliary agent is one or more of Fe, Ce and Zr, and the auxiliary agent accounts for the whole catalyst.
  • the mass fraction is 0.05% to 5%.
  • Coating of the carrier coating The coating colloid is applied to the wire mesh skeleton by dipping, and the coated metal skeleton is baked at 1200 ° C for 1 to 8 hours to firmly adhere the carrier coating. On the surface of the wire mesh skeleton;
  • the metal skeleton is a cylinder, a rectangular parallelepiped, or a triangular prism.
  • the auxiliary agent in the step (2) is one or more of Fe, Ce and Zr, and the coating colloid is a kind of pseudo-boehmite, silica sol and titanium oxide powder containing an auxiliary agent. Or a few dissolved in deionized water, adjusted to pH 2 ⁇ 6 by dilute nitric acid or dilute hydrochloric acid, the concentration of dilute nitric acid or dilute hydrochloric acid is 0.1 ⁇ 0.2mol/L.
  • the Pd salt in the step (4) is PdCl 2 or Pd(N0 3 ) 2
  • the auxiliary metal salt is Fe(N0 3 ) 2 , Ce(N0 3 ) 2 , Zr(N0 3 ) 2 , FeCl. 2 , CeCl 2 or ZrCl 2 .
  • the concentration of the dilute nitric acid or the dilute hydrochloric acid in the step (4) is 0.1 to 0.2 mol/L.
  • the catalyst of the present invention is reduced by a mixed gas of CO and N 2 before use.
  • the volume fraction of CO in the mixed gas is 5 to 50%
  • the reduction temperature is 150 to 300 ° C
  • the reduction pressure is normal pressure
  • the reduction time is 1 to 12 hours.
  • the catalyst of the invention can also be reduced by a mixed gas of H 2 and N 2 , the reduction temperature is 150-300 ° C, the reduction pressure is normal pressure, and the reduction time is 1 to 12 hours.
  • the CO coupling reaction method for synthesizing oxalate mainly involves two reactions.
  • the first reaction is a CO coupling reaction.
  • the reaction was a strongly exothermic reaction with a heat of reaction of 181 kJ/mol.
  • the reactants are CO and decyl nitrite, the product is didecyl oxalate and NO, and the chemical reaction equation is as follows, wherein R represents a methyl group, an ethyl group, or a propyl group.
  • the second reaction is the regeneration reaction of decyl nitrite.
  • the reactants are mercapto alcohol, oxygen and by reaction
  • the obtained NO, the product is decyl nitrite and water.
  • the chemical reaction equation is as follows. Among them, decyl nitrite is the reactant of the reaction (1).
  • the catalyst according to the present invention is applied to the reaction (1).
  • the reaction (1) is characterized by rapid reaction and high calorific value of the reaction; the reaction pressure is 300 to 500 kPa, and the reaction temperature is 110 to 160 °C. Therefore, from the viewpoint of removing the heat of reaction, the reactor form of the reaction (1) is usually selected from a tubular fixed bed having a diameter of 32 to 40 mm.
  • the catalyst applied to the reaction (1) is mainly composed of granular Pd/a-Al 2 0 3 , and the particle shape is mainly circular, and the particle equivalent diameter is about 3 to 5 mm.
  • the height of the catalyst bed in the reactor tubes is about 4 to 6 meters. Since the lower reaction pressure of the reaction W results in a higher catalyst bed lamination drop, the pressure drop is usually 70 to 100 kPa. Higher bed lamination drops in industrial applications will result in increased cycle compressor pressure ratios and increased operating costs.
  • the honeycomb structured catalyst is characterized by a series of parallel channels that are not interconnected in the axial direction. Therefore, the honeycomb structured catalyst is not only suitable for rapid reaction, but also can effectively reduce the catalyst bed lamination drop. However, this feature also causes the radial heat transfer capacity of the catalyst bed to decrease. The difference between the center temperature of the catalyst bed and the outer edge temperature can reach more than 50 °C, and the radial temperature difference is much higher than that of the conventional random catalyst bed; This causes the catalyst bed to fly to temperature.
  • the wire mesh skeleton catalyst according to the claims of the present invention is capable of effectively reducing the bed lamination drop and the radial temperature difference of the catalyst bed.
  • the wire mesh skeleton catalyst is characterized by not only an axially flat passage but also a rich radial passage. When the gas flows through these channels, a micro-turbulent flow is formed inside the cells, effectively enhancing the heat transfer in the radial direction of the catalyst bed.
  • the external specific area of the catalyst is greatly increased, so that it is more advantageous to apply to the rapid reaction system than the other forms of the catalyst; it can effectively reduce the use of precious metals in the catalyst while ensuring the equivalent activity. the amount.
  • the catalyst of the invention is applied to a 10-ton/year scale single-tube reaction device for reacting CO with methyl nitrite to synthesize dimethyl oxalate (the catalyst bed height is 4 meters), and is good. effect.
  • the reaction pressure is 200 ⁇ 500kPa
  • the reaction temperature is 110 ⁇ 160°C
  • GHSVSOOO-SOOOh 1
  • the activity of the catalyst did not decrease, the average conversion rate of methyl nitrite was 90-95%, and the average space-time yield of dimethyl oxalate was as high as 1200 g/l.cat.h.
  • the bed lamination drop is reduced from 80 kPa to 15 kPa; the radial temperature difference is reduced from 30 ° C to 2 ° C ; in the case of the same Pd metal usage
  • the average space time yield of dimethyl oxalate was increased from 700 g/l.cat.h to 1200 g/l.cat.h. detailed description
  • a method for preparing a wire mesh skeleton catalyst for synthesizing dimethyl oxalate comprises the following steps:
  • An alloy steel wire mesh with a hole size of 40 mesh is selected, firstly punched into a corrugated shape by a punching machine, and then rolled into a catalyst metal skeleton having a height of 10 cm and a diameter of 2.5 cm by a rolling machine.
  • the coating colloid is applied to the wire mesh skeleton by dipping.
  • the coated metal skeleton was fired at 1200 ° C for 5 hours to firmly adhere the carrier coating to the surface of the wire mesh skeleton.
  • PdCl 2 , ZrCl 2 and water were formulated into a palladium nitrate solution, and the pH of the precursor solution was adjusted to 10 with ammonia water.
  • the wire mesh skeleton having the coating structure is placed in the prepared precursor solution, and the active component Pd and the auxiliary agent Zr are supported on the surface of the carrier coating by an immersion method.
  • the catalyst after the completion of the impregnation was dried at 120 ° C for 12 hours, followed by baking at 550 ° C for 6 hours.
  • the obtained catalyst was calculated as A, wherein the catalyst Pd loading was 0.1% by mass of the entire catalyst, and the loading of Zr was 0.05%.
  • Catalyst A The performance of Catalyst A was tested.
  • a small spherical Pd/a-Al 2 O 3 catalyst was used as a comparative sample.
  • the catalyst had a Pd loading of 0.1%, a loading of Zr of 0.05%, and a particle diameter of 4 mm.
  • the catalyst was counted as 8.
  • a and B catalysts were evaluated using the same size fixed bed reactor, and the reactor was 25 cm in height and 20 cm in height. Both A and B catalyst loading heights are 10 cm.
  • Raw material CO and methyl nitrite The ratio is 2: 1.
  • the space velocity of Catalyst A was 7000/h
  • the space velocity of Catalyst B was 3000/h. Table 1 Catalyst performance evaluation results
  • Catalyst A is superior to small spherical Pd/a-Al 2 0 3 catalyst in radial temperature difference, oxalate space-time yield, conversion rate and Pd utilization rate.
  • a method for preparing a catalyst for synthesizing oxalate by a CO coupling reaction comprising the steps of:
  • Coating of the carrier coating The coating colloid is applied to the wire mesh skeleton by dipping, and the coated metal skeleton is baked at 1200 ° C for 1 hour to firmly adhere the carrier coating to the metal. On the surface of the wire mesh skeleton, the mass of the carrier coating accounts for 1% of the mass of the entire catalyst;
  • the resulting catalyst was reduced using a mixed gas of CO and N 2 before use.
  • the volume fraction of CO in the mixed gas is 5 ⁇ 50%
  • the reduction temperature is 150 ⁇ 300°C
  • the reduction pressure is normal pressure
  • the reduction time is 1 ⁇ 12. hour.
  • a method for preparing a catalyst for synthesizing oxalate by a CO coupling reaction comprising the steps of:
  • Coating of the carrier coating The coating colloid is applied to the wire mesh skeleton by the dipping method, and the coated metal skeleton is baked at 1200 ° C for 1 to 8 hours to firmly adhere the carrier coating. On the surface of the wire mesh frame, the mass of the carrier coating accounts for 1% ⁇ 55% of the mass of the whole catalyst ;
  • the obtained catalyst is reduced by a mixed gas of 11 2 and N 2 , the reduction temperature is 150 to 300 ° C, the reduction pressure is normal pressure, and the reduction time is 1 to 12 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un catalyseur de synthèse d'oxalate par une réaction de couplage de CO et un procédé de fabrication dudit catalyseur. Le catalyseur présente une maille métallique comme ossature, une couche de revêtement de support est appliquée sur une surface de la maille métallique, et un composant actif et des additifs sont chargés sur une surface du revêtement de support. A l'aide du catalyseur, sous la condition préalable que l'activité est assurée, la quantité de composants actifs de métaux nobles par unité de volume du catalyseur est réduite, la chute de pression du lit de catalyseur est diminuée, et la température radiale du lit de catalyseur est abaissée, permettant ainsi de résoudre le problème de transfert thermique dans le procédé de réaction et de l'emballement de la température qui se produit facilement lorsqu'un catalyseur en nid d'abeilles classique est utilisé dans le système réactionnel.
PCT/CN2012/074052 2011-05-20 2012-04-14 Catalyseur de synthèse d'oxalate par une réaction de couplage de co et procédé de fabrication dudit catalyseur Ceased WO2012159510A1 (fr)

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JP2014510647A JP2014518760A (ja) 2011-05-20 2012-04-14 Ｃｏカップリング反応によるシュウ酸エステルの合成に用いる触媒およびその製造方法

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CN201110131440.7A CN102784640B (zh) 2011-05-20 2011-05-20 用于co偶联反应合成草酸酯的催化剂及其制备方法
CN201110131440.7 2011-05-20

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Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
CN106914240A (zh) * 2015-12-25 2017-07-04 上海华谊能源化工有限公司 一种co气相偶联合成草酸酯的催化剂及其制备方法与应用
CN105879924A (zh) * 2016-04-27 2016-08-24 北京石油化工学院 一种负载型贵金属催化剂还原预处理的方法
CN112619656A (zh) * 2020-12-17 2021-04-09 湖北楚儒同位素科技有限公司 一种以铜质丝网波纹填料为载体的一氧化碳转化催化剂
CN114029005B (zh) * 2021-11-30 2024-01-30 华东理工大学 一种催化剂径向分布的堆积方法及轴向反应器

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EP0105480A1 (fr) * 1982-09-30 1984-04-18 Union Carbide Corporation Procédé de préparation d'un diester de l'acide oxalique
JPH03154617A (ja) * 1989-11-13 1991-07-02 Daido Steel Co Ltd 排ガス浄化装置
CN101015800A (zh) * 2007-02-07 2007-08-15 大连理工大学 催化还原氮氧化物的蜂窝状金属丝网载体催化剂及其制法
CN101049577A (zh) * 2007-02-07 2007-10-10 大连理工大学 一种具有氧化铝涂层的蜂窝状金属丝网载体及其制备方法
CN101444734A (zh) * 2008-12-12 2009-06-03 无锡威孚环保催化剂有限公司 净化非道路用小型柴油发动机废气的催化剂及制备方法
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

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JP5110249B2 (ja) * 2005-08-11 2012-12-26 戸田工業株式会社 炭化水素を分解する触媒、該触媒を用いた炭化水素の分解方法及び水素の製造方法、並びに発電システム
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JP5335505B2 (ja) * 2009-03-19 2013-11-06 旭化成ケミカルズ株式会社 貴金属担持物及びそれを触媒として用いるカルボン酸エステルの製造方法

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
EP0105480A1 (fr) * 1982-09-30 1984-04-18 Union Carbide Corporation Procédé de préparation d'un diester de l'acide oxalique
JPH03154617A (ja) * 1989-11-13 1991-07-02 Daido Steel Co Ltd 排ガス浄化装置
CN101015800A (zh) * 2007-02-07 2007-08-15 大连理工大学 催化还原氮氧化物的蜂窝状金属丝网载体催化剂及其制法
CN101049577A (zh) * 2007-02-07 2007-10-10 大连理工大学 一种具有氧化铝涂层的蜂窝状金属丝网载体及其制备方法
CN101444734A (zh) * 2008-12-12 2009-06-03 无锡威孚环保催化剂有限公司 净化非道路用小型柴油发动机废气的催化剂及制备方法
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

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CN102784640A (zh) 2012-11-21
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