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WO2021074028A1 - Nouveau système de réacteur pour la production d'anhydride maléique par oxydation catalytique de n-butane - Google Patents

Nouveau système de réacteur pour la production d'anhydride maléique par oxydation catalytique de n-butane Download PDF

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Publication number
WO2021074028A1
WO2021074028A1 PCT/EP2020/078406 EP2020078406W WO2021074028A1 WO 2021074028 A1 WO2021074028 A1 WO 2021074028A1 EP 2020078406 W EP2020078406 W EP 2020078406W WO 2021074028 A1 WO2021074028 A1 WO 2021074028A1
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WIPO (PCT)
Prior art keywords
reactor
butane
catalyst particles
reactor tube
tube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2020/078406
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German (de)
English (en)
Inventor
Sebastian Boecklein
Gerhard Mestl
ADLER (GEB. WALDSCHUETZ), Anna
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Clariant International Ltd
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Clariant International Ltd
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Priority to CN202080068767.1A priority Critical patent/CN114450081A/zh
Publication of WO2021074028A1 publication Critical patent/WO2021074028A1/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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/55—Cylinders or rings
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00548—Flow
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00654—Controlling the process by measures relating to the particulate material
    • B01J2208/00672—Particle size selection
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00805—Details of the particulate material
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/06—Details of tube reactors containing solid particles
    • B01J2208/065—Heating or cooling the reactor

Definitions

  • the invention relates to a reactor system for the production of maleic anhydride by catalytic oxidation of n-butane, comprising at least one reactor tube with an inner diameter greater than 23 mm, which is filled with catalyst particles, characterized in that the ratio of the surface area in the at least one filled reactor tube the Kata lysatorp motherboard per unit volume to the cross-sectional area of the reactor tube is less than 1.5 cm 3 .
  • the invention also relates to a method for producing maleic anhydride by catalytic oxidation of n-butane, a mixture of oxygen and n-butane being passed through a reactor system according to the invention and the at least one reactor tube being at an elevated temperature.
  • the invention also relates to the use of a reactor tube with an inner diameter greater than 23 mm for the production of maleic anhydride by the selective catalytic oxidation of n-butane with catalyst particles which have a geometric surface area of more than 2 cm 2 .
  • Maleic anhydride is a chemical intermediate of great economic importance. It is used, for example, in the production of alkyd and polyester resins, either alone or in combination with other acids. In addition, it is also a versatile intermediate for chemical synthesis, for example for the synthesis of g-butyrolactone, tetrahydrofuran and 1,4-butanediol, which in turn are used as solvents or to polymers such as polytetrahydrofuran or Polyvinylpyrrolidone, can be further processed.
  • maleic anhydride (MA) from n-butane takes place by selective gas phase oxidation in cooled tube bundle reactors, with catalyst particles being filled as VPO catalysts into the reactor tubes and forming a catalyst bed there. Since a large amount of heat is released in the course of the reaction (n-butane to MA: -1260 kJ / mol, n-butane to CO2: 2877 kJ / mol), the reaction is usually carried out in tube bundle reactors with tube inner diameters of 21 mm carried out in order to be able to dissipate this heat via the pipe wall into the cooling medium consisting of a molten salt.
  • EP 2643086 A1 discloses shaped catalyst bodies for the catalytic conversion of n-butane to maleic anhydride in fixed bed reactors, the shaped catalyst body being designed as a cylinder with a base, a cylinder surface, a cylinder axis and at least one continuous opening running parallel to the cylinder axis and the base of the cylinder at least has four praise, wherein a shaped catalyst body enveloping geometric base body is a prism which has a prism base with a length and a width, the length being greater than the width.
  • the object is therefore to provide a reactor system, in particular a tube bundle reactor, for the catalytic oxidation of n-butane to maleic anhydride, which has reactor tubes with an inside diameter greater than 23 mm, with which a thermally stable operation and a high MA yield is made possible.
  • the object is achieved by a reactor system for the production of maleic anhydride by catalytic oxidation of n-butane, comprising at least one reactor tube with an inner diameter greater than 23 mm, which is filled with catalyst particles, characterized in that the ratio of the geometric surface area of the catalyst particles per unit volume to the cross-sectional area of the reactor tube is less than 1.5 cm 3 .
  • the object is achieved by a method for producing maleic anhydride by the catalytic oxidation of n-butane, a mixture comprising n-butane and oxygen being passed through the reactor concept according to the invention.
  • the object is also achieved by the use of catalyst particles which have a geometric surface area of more than 2 cm 2 in a reactor tube with an inner diameter greater than 23 mm for the production of maleic anhydride by the selective catalytic oxidation of n-butane.
  • the part of the reactor tube filled with catalyst particles typically has a length of 3 to 8 m, preferably 4 to 6 m.
  • the catalytic oxidation of n-butane to maleic anhydride takes place, so that the temperature in this area has to be controlled, ie tempered.
  • the reactant gas which must contain n-butane and oxygen, contains, for example, a mixture of between 0.2 to 10% by volume of n-butane and 5 to 50% by volume of oxygen.
  • the feed gas typically consists of a mixture of 0.5 to 3% by volume of n-butane, 10 to 30% by volume of oxygen and, moreover, of an inert gas such as nitrogen and 1 to 4% by volume of water.
  • the reactant gas contains air and the corresponding amount of n-butane and optionally water is added.
  • small amounts of 0.5 to 5 ppm or 1 to 3 ppm, based on the gas volume, of organic phosphoric acid esters such as trimethyl phosphate or triethyl phosphate can be present in the starting gas in order to compensate for the loss of phosphate from the catalyst.
  • the reactant gas is passed into the reactor tube (typically from below) and comes into contact with the reactor tube at an elevated temperature in the part of the reactor tube filled with catalyst particles, with n-butane being oxidized to maleic anhydride.
  • reactor tubes which can be temperature-controlled individually or together. Since the selective oxidation of n-butane to maleic anhydride is an exothermic reaction, excess heat has to be dissipated and, at the same time, it has to be ensured that the reactor tubes are at the necessary reaction temperature.
  • the temperature is preferably controlled by means of a salt bath (for example a eutectic of potassium nitrate and sodium nitrite, approx. In a ratio of 1: 1) in which a large number of reactor tubes are let.
  • the salt bath typically has a temperature between 380 ° C and 430 ° C.
  • the reaction can be carried out at a low salt bath temperature between 400 ° C. and 420 ° C., which leads to increased thermal stability and increased selectivity.
  • a temperature profile develops in the axial direction within the reactor tube, with an area with maximum temperature (“hotspot”) being created in the first third of the reactor tube.
  • the maximum temperature in the reactor tube is 430 ° C to 460 ° C, according to the invention, a maximum temperature between 440 ° C and 450 ° C is preferred.
  • the catalyst particles preferably contain a vanadyl pyrophosphate phase (VPO phase) and can be supported or else consist entirely of the VPO phase.
  • VPO phase can have the usual dopings, including in particular molybdenum and / or alkali metals, as described, for example, in DE 10 2014 004786 A1.
  • the ratio of the geometric surface area of the catalyst particles per unit volume to the cross-sectional area of the reactor tube in the filled reactor tube must be less than 1.5 cm 3 .
  • This condition applies to a reactor tube inside diameter of more than 23 mm and otherwise typical reaction conditions and catalyst geometries must be met if the catalyst particles have a geometric surface area of more than 2 cm 2 .
  • the inner diameter of the reactor tube is greater than or equal to 24 mm, more preferably greater than or equal to 25 mm.
  • the reactor tube typically has a wall thickness of 1 to 2 mm, so that the outer diameter of the reactor tube is correspondingly larger.
  • the catalyst particles in the reactor tube have a bulk density of less than 0.8 g / cm 3, in particular less than 0.7 g / cm 3
  • Preferred catalyst particles for use in the reactor concept according to the invention are those which are described in EP 2643086 A1. These preferred catalyst particles are particularly characterized in that each individual catalyst particle is designed as a cylinder with an outer base surface [1], a cylinder surface [2], a cylinder axis and at least one continuous opening [3] running parallel to the cylinder axis and the Outer base surface [1] of the cylinder has at least four lobes [4a, 4b, 4c, 4d], a geometric base body surrounding the catalyst particles being a prism which has a prism base surface with a length and a width, the length being greater than the width , the lobes [4a, 4b, 4c, 4d] being enclosed by prism corners of the prism base area.
  • the geometric surface area of the catalyst particles Op does not mean the specific BET surface area of the catalyst material, but the geometric outer surface of a catalyst particle, i.e. the surface that would result if the catalyst particle were a solid, non-porous body.
  • the geometric outer surface of the catalyst particle results solely from its geometric dimensions.
  • the specific BET surface area is the inner surface of the porous powder per gram of catalyst material.
  • An axial section of the reactor tube is understood to be a section which is delimited by two fictitious lines running perpendicular to the longitudinal direction of the reactor tube, so that the imaginary fictitious cut surfaces are circular.
  • OK (SD / m P ) * Op.
  • OK / QR ⁇ 1.5 cnr 3 is preferably (OK / QR) S 1. 45 cnr 3 , more preferably ⁇ 1.40 cnr 3 and most preferably ⁇ 1.35 cnr 3 .
  • Table 1 summarizes the economic advantages resulting from the reactor concept according to the invention compared to the prior art.
  • a reactor tube with an internal diameter of 21 mm with a space-time velocity of 2,000 h -1 (with a bed length of 5.5 m) and a butane concentration of 1.9% by volume of n-butane in the reactant gas stream is regarded as the state of the art.
  • the experimentally determined yield of MA in combination with the space-time velocity results in a productivity of MA per tube and per unit of time. This productivity can be influenced by varying the space-time velocity and the n-butane concentration via the respective resulting MA yield.
  • Figure 4 Representations of the preferred catalyst particle, the “double alpha form” from four different perspectives.
  • the granulate is pressed with a rotary tablet press to the desired tablet shape and side compressive strength:
  • a double alpha shape was pressed with a height of 5.6 mm, a length of 6.7 mm, a width of 5.8 mm and an internal hole diameter of 2.1 mm.
  • These catalyst particles have a geometric surface area of 2.37 cm 2 , a volume of 0.154 cm 3 and a mass of 0.24 g.
  • a filling density of 0.60 to 0.62 g / cm 3 results, in a 25 mm reactor there is a filling density of 0.65 to 0.67 g / cm 3 .
  • catalyst particles were pressed in the usual cylindrical shape with a height of 5.6 mm, an outside diameter of 5.5 mm and a central axial opening with a diameter of 2.3 mm.
  • These bodies have a geometric surface area of 1.77 cm 2 , a volume of 1.11 cm 3 and a mass of 0.18 g.
  • the result is a filling density of 0.72 to 0.76 g / cm 3 .
  • Activation to pyrophosphate The activation, which produces vanadium pyrophosphate, is carried out in a retort built into a programmable oven under controlled conditions. The calcined tablets are poured evenly into the retort and the retort is tightly sealed. The catalyst is then activated in a moist air-stick mixture (50% absolute humidity) first at over 300 ° C. for 5 h, then at over 400 ° C. for 9 h.
  • the catalytic test reactions were carried out in a tubular reactor with 21 mm internal diameter and 25 mm internal diameter and a bed length of 5.5 m in each case under comparable conditions.
  • the feed stream consisted of 1.9% by volume of n-butane, diluted in air, 2.5% by volume of water and about 2 ppm of trimethyl phosphate.
  • the space-time velocity (GHSV expressed in h 1 ) was 2,000 h 1 and 2,200 h 1 in the reactor with an internal diameter of 21 mm.
  • the space-time velocity in the reactor with an internal diameter of 25 mm was 1,411 h 1 and 1,552 h 1 .
  • Space-time velocity is understood here to mean the inverse of time in which the gas that has flowed through the reactor corresponds to the empty volume of the reactor tube under normal conditions.
  • the yield of maleic anhydride is given in percent by weight (% by weight) based on the weight of the n-butane used.
  • Figure 1 shows the results of the catalytic test reaction using a reactor with

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'invention concerne un système de réacteur pour la production d'anhydride maléique par oxydation catalytique de n-butane, comprenant au moins un tube de réacteur ayant un diamètre intérieur supérieur à 23 mm, qui est rempli de particules de catalyseur, caractérisé en ce que, dans le tube de réacteur rempli, le rapport de la zone de surface géométrique des particules de catalyseur par volume unitaire à la surface de section transversale du tube de réacteur est inférieur à 1,5 cm-3. L'invention concerne en outre un procédé de production d'anhydride maléique par oxydation catalytique de n-butane, un mélange d'oxygène et de n-butane étant amené à travers un système de réacteur selon l'invention et l'au moins un tube de réacteur étant à température élevée. L'invention concerne en outre l'utilisation d'un tube de réacteur présentant un diamètre intérieur supérieur à 23 mm pour produire de l'anhydride maléique par oxydation catalytique sélective de n-butane au moyen de particules de catalyseur présentant une zone de surface géométrique supérieure à 2 cm².
PCT/EP2020/078406 2019-10-15 2020-10-09 Nouveau système de réacteur pour la production d'anhydride maléique par oxydation catalytique de n-butane Ceased WO2021074028A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202080068767.1A CN114450081A (zh) 2019-10-15 2020-10-09 通过催化氧化正丁烷制备马来酸酐的新反应器系统

Applications Claiming Priority (2)

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DE102019127788.4 2019-10-15
DE102019127788.4A DE102019127788A1 (de) 2019-10-15 2019-10-15 Neues Reaktorsystem für die Herstellung von Maleinsäureanhydrid durch katalytische Oxidation von n-Butan

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WO2021074028A1 true WO2021074028A1 (fr) 2021-04-22

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DE (1) DE102019127788A1 (fr)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993001155A1 (fr) * 1991-07-08 1993-01-21 Monsanto Company Procede de production a haut rendement d'anhydride maleique
DE102010006723A1 (de) * 2010-02-03 2011-08-04 Süd-Chemie AG, 80333 Reaktorvorrichtung und Verfahren zur Optimierung der Messung des Temperaturverlaufs in Reaktorrohren
EP2643086A1 (fr) * 2010-11-22 2013-10-02 Süd-Chemie IP GmbH & Co. KG Corps moulé de catalyseur pour des réacteurs à lit fixe à écoulement continu

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4342699A (en) * 1981-02-23 1982-08-03 Standard Oil Company (Indiana) Process for production of maleic anhydride
HUT63973A (en) * 1990-10-04 1993-11-29 Monsanto Co Formed oxidation catalyzer-devices for producing maleine-acid-anhydride
JPH0531351A (ja) * 1991-07-29 1993-02-09 Mitsubishi Rayon Co Ltd 触媒の充填方法
ZA200200049B (en) * 2001-01-25 2002-07-16 Nippon Catalytic Chem Ind Fixed-bed shell-and-tube reactor and its usage.
JP4334797B2 (ja) * 2001-01-25 2009-09-30 株式会社日本触媒 固定床多管式反応器への固体粒状物の充填方法
KR101392580B1 (ko) * 2007-01-19 2014-05-21 바스프 에스이 그의 활성 덩어리가 다원소 산화물인 촉매 성형체의 제조 방법
JP5450591B2 (ja) * 2009-03-09 2014-03-26 株式会社日本触媒 酸化有機化合物の製造方法
DE102014004786B4 (de) * 2014-04-02 2021-09-30 Clariant International Ltd. Alkalimetall-modifizierter Vanadium-Phosphor-Oxid (VPO)-Katalysator

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993001155A1 (fr) * 1991-07-08 1993-01-21 Monsanto Company Procede de production a haut rendement d'anhydride maleique
DE102010006723A1 (de) * 2010-02-03 2011-08-04 Süd-Chemie AG, 80333 Reaktorvorrichtung und Verfahren zur Optimierung der Messung des Temperaturverlaufs in Reaktorrohren
EP2643086A1 (fr) * 2010-11-22 2013-10-02 Süd-Chemie IP GmbH & Co. KG Corps moulé de catalyseur pour des réacteurs à lit fixe à écoulement continu

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DE102019127788A1 (de) 2021-04-15
CN114450081A (zh) 2022-05-06

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