WO2013125639A1 - Dispositif de réaction en phase gazeuse - Google Patents

Dispositif de réaction en phase gazeuse Download PDF

Info

Publication number
WO2013125639A1
WO2013125639A1 PCT/JP2013/054343 JP2013054343W WO2013125639A1 WO 2013125639 A1 WO2013125639 A1 WO 2013125639A1 JP 2013054343 W JP2013054343 W JP 2013054343W WO 2013125639 A1 WO2013125639 A1 WO 2013125639A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas phase
plating
molybdenum
phase reaction
oxide catalyst
Prior art date
Application number
PCT/JP2013/054343
Other languages
English (en)
Japanese (ja)
Inventor
慎二 岩出
健治 末岡
広志 亀尾
Original Assignee
三菱レイヨン株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2012036315A external-priority patent/JP2015086134A/ja
Priority claimed from JP2012035935A external-priority patent/JP2015085207A/ja
Application filed by 三菱レイヨン株式会社 filed Critical 三菱レイヨン株式会社
Publication of WO2013125639A1 publication Critical patent/WO2013125639A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • 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
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1809—Controlling processes
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • 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
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00141—Coils
    • 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
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00902—Nozzle-type feeding elements
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to a gas phase reactor.
  • nitrile As a method for producing nitrile, a method of obtaining an unsaturated nitrile such as acrylonitrile by reacting olefin such as propylene or paraffin such as propane with ammonia and oxygen by an ammoxidation method is known, and as a catalyst used in this reaction, A metal oxide catalyst containing molybdenum is used.
  • olefin such as propylene or paraffin such as propane
  • olefin such as propylene or paraffin such as propane
  • ammonia and oxygen an ammoxidation method
  • a metal oxide catalyst containing molybdenum is used as a catalyst used in this reaction.
  • molybdenum in the metal oxide catalyst is liberated as a molybdenum compound such as molybdenum hydroxide when water generated as a by-product in the ammoxidation method increases in the reactor.
  • molybdenum trioxide crystals are precipitated at a site such as a cooling pipe in the gas phase reactor and
  • the metal oxide catalyst loses its catalytic activity and is wasted, and the precipitated molybdenum trioxide crystals cover the cooling pipe to lower the thermal conductivity or block the pipe. In this case, there are adverse effects such as increasing the pressure loss and corroding the base material itself.
  • Patent Document 1 describes a method of introducing a powder into a reaction gas and removing the deposits attached to the heat exchanger with this powder.
  • Patent Document 2 describes a method of suppressing a decrease in catalyst activity and a change in particle size distribution by installing an indirect heat exchanger in a catalyst dilute layer at the top of the reactor.
  • Patent Document 1 is not practical because the powder wears not only the molybdenum oxide but also the apparatus, and it takes much time to separate and remove the powder downstream. Furthermore, in the method of Patent Document 2, the amount of adhesion is not sufficiently reduced, and it is necessary to cool the indirect heat exchanger with another cooling medium, which is inefficient.
  • the present invention relates to adhesion of molybdenum oxide to a contact surface of a vapor phase reaction apparatus that performs vapor phase oxidation using an oxide catalyst containing molybdenum and contacts with a molybdenum compound released from the metal oxide catalyst. It aims at suppressing efficiently.
  • the present invention relates to a gas phase reactor for causing a reaction using a metal oxide catalyst containing molybdenum, wherein the surface roughness of the contact surface with which the molybdenum compound released from the metal oxide catalyst contacts is a stylus type surface.
  • the center line average roughness (Ra) in the roughness measurement method is 0.1 ⁇ m or more and 5 ⁇ m or less, and this contact surface was covered with a film formed by thermal spraying or plating, thereby solving the above-mentioned problem. It is.
  • the contact surface is released from the metal oxide catalyst by forming a metal film by thermal spraying or plating.
  • the adhesion of the molybdenum compound can be suppressed.
  • adhesion of a molybdenum compound released from the metal oxide catalyst can be further suppressed.
  • the present invention relates to a gas phase reaction apparatus for causing a reaction using a metal oxide catalyst containing molybdenum.
  • Examples of the reaction performed using the above metal oxide catalyst containing molybdenum include a reaction for producing acrylonitrile from propylene and ammonia by an ammoxidation method, and production of acrylic acid by vapor phase oxidation of propylene.
  • the molybdenum-containing metal oxide catalyst only needs to have catalytic ability for the above reaction.
  • the reaction for producing the above acrylonitrile includes a Mo—Bi-based catalyst.
  • Me II represents a II-valent metal such as Co or Ni
  • Me III represents a III-valent metal such as Fe or Cr
  • Me I represents an I-valent metal such as Na or K.
  • the reaction is generally carried out by contacting the metal oxide catalyst in the form of fine particles as a fluidized bed with a gas phase reactant.
  • a gas phase reactor for producing acrylonitrile by the above-described ammoxidation method is shown in FIG.
  • Air a is introduced into the main body 11 of the gas phase reaction apparatus from the lower air introduction pipe 12 and blown out from the blow-out port 13 to float the catalyst 14.
  • a mixed gas b of propylene and ammonia is introduced from the raw material introduction pipe 15 as the above-mentioned reactant, and these are oxidized with oxygen in the air to obtain 1 equivalent of acrylonitrile and 3 equivalents of water.
  • the above reaction is performed while cooling the mixed gas inside the main body 11 by the cooling coil 16 through which the refrigerant d has passed.
  • Acrylonitrile produced by the reaction in the gas phase reactor is separated from the catalyst by the cyclone 19 and extracted from the product discharge pipe 17 as a reaction gas c containing impurities such as unreacted ammonia and by-product acrylic acid. It is.
  • the reaction gas c is cooled by the heat exchanger 18 and then sent to the ammonia absorption / separation system and the acrylonitrile purification system.
  • contact surface As a contact surface (hereinafter, simply referred to as “contact surface”) where the molybdenum compound released from the metal oxide catalyst contacts, for example, cooling such as the cooling coil 16 or the heat exchanger 18 is performed. And the inner surface of the part where the flow of gas changes, such as the surface of the part that is likely to precipitate due to, or the part where the pipe entrance / exit or the thickness of the pipe changes. Molybdenum compounds liberated from the catalyst as hydroxides by water generated by the reaction tend to adhere and grow as molybdenum oxide crystals on these contact surfaces. As a method for suppressing them as much as possible, a method is conceivable in which the surface roughness of the contact surface is set within a predetermined range and then covered with a metal film.
  • the gas phase reactor in the present invention is connected not only to the inside of the main body 11 of the gas phase reactor but also to the main body 11 of the gas phase reactor, and the main body 11 in contact with the released molybdenum compound. Also includes external piping and heat exchanger 18.
  • the above surface roughness is a roughness measured by a stylus type surface roughness measuring method, and the center line average roughness (Ra) is required to be 5 ⁇ m or less, and preferably 1 ⁇ m or less. If it is larger than 5 ⁇ m, it is difficult to suppress adhesion of the molybdenum compound even if it is covered with a metal film. On the other hand, 0.1 ⁇ m is sufficient as the lower limit of the surface roughness. Although it may be smaller than 0.1 ⁇ m, it is more difficult to prepare a member having such a contact surface.
  • a mechanical polishing method in which a metal surface is smoothed by mechanically or manually scraping a sandpaper, a grindstone, or an abrasive containing fine particles.
  • Electrolytic polishing method in which the metal surface is submerged in an acidic solution and the surface is melted and smoothed by passing an electric current, and a chemistry that provides a smooth metal surface by immersing in a solution of various compositions without applying an electric current.
  • An example is a polishing method.
  • the contact surface having a surface roughness within the above range is covered with a metal film.
  • a metal film examples include thermal spraying and plating.
  • the above-mentioned thermal spraying refers to forming a coating of the above material on the surface by bringing the metal forming the coating into a molten or semi-molten state and colliding with the contact surface.
  • Examples of the plating method include plating methods such as brush plating, electroplating, and electroless plating.
  • a plating treatment step a plating treatment method having a step of immersing in a plating solution, that is, a plating treatment method by an electroplating method or an electroless plating method is preferable, and a plating treatment method by an electroless plating method is more preferable.
  • the brush plating method is a method in which a plating object is immersed in an electrolytic solution containing plating metal ions and this electrolytic solution is applied to the plating object.
  • This brush is generally made by winding a fibrous material around a stainless steel electrode body so that the electrode does not directly touch the object to be plated and the electrolyte is held on the fiber. Then, this is connected to the positive pole of the low voltage power source, and the plating object is connected to the negative pole to perform the electroplating process.
  • the electroplating method is a conductive electrolyte containing a metal salt for plating an object to be plated, that is, dipped in a plating solution, and electricity is passed between a pair of electrodes immersed in the plating solution, to the surface of the object to be plated. This is a method of depositing a metal film to be plated.
  • the electroless plating method is immersed in a plating solution containing a metal salt and a reducing agent for plating an object to be plated, not by electrons due to energization, but by electrons released by oxidation of the reducing agent contained in the plating solution, This is a method of depositing a metal film to be plated on an object to be plated.
  • the obtained plating film has a uniform thickness regardless of the shape and type of the material.
  • the plating object is immersed in the plating solution, so that the plating film can be formed while maintaining the surface roughness of the object. Thereby, it becomes possible to suppress adhesion of the molybdenum compound released from the metal oxide catalyst. And when the film thickness of a plating film is thickened, adhesion of the said molybdenum compound can be suppressed more.
  • Examples of the metal constituting the metal film formed by the above-described thermal spraying or plating treatment include metals such as molybdenum, zinc, copper, silver, gold, titanium, aluminum, chromium, nickel, INCONEL (registered trademark, “Inconel”).
  • Alloys containing nickel-chromium-molybdenum-iron such as INCOLOY (registered trademark, referred to as "Incoloy"), alloys containing aluminum-chromium-iron, such as HASTELLOY (registered trademark), Hastelloy Alloys containing nickel-molybdenum-tungsten, such as MONEL (registered trademark, referred to as “Monel”), alloys containing nickel-copper, cobalt-chromium, such as stellite®, etc. Alloys containing tungsten, stainless steel made of nickel-chromium-iron such as SUS304 , Cermets, chromium carbide, titanium oxide and the like, can be used alone or in combination.
  • the metal constituting the plating film includes nickel, chromium, zinc, gold, silver and the like.
  • the plating film formed by electroplating is an alloy film of nickel and phosphorus, and the plating film formed by electroless plating is a pure nickel film.
  • the gas phase reactor according to the present invention uses a metal oxide catalyst containing molybdenum.
  • the amount of molybdenum oxide deposited can be suppressed, so the consumption of catalyst can be suppressed, the cooling effect can be reduced by the coating of the parts, and the corrosion of the substrate can be suppressed.
  • a manufacturing plant using an ammoxidation method such as acrylonitrile It can be operated more efficiently.
  • Production Example 3 The surface of Production Example 1 was subjected to nickel plating using an electroless plating method.
  • the surface roughness (Ra) was measured by a stylus type surface roughness measuring instrument and found to be 1.09 ⁇ m.
  • Production Example 4 The surface of Production Example 2 was subjected to nickel plating using an electroless plating method.
  • the surface roughness (Ra) was measured with a stylus type surface roughness measuring instrument and found to be 0.11 ⁇ m.
  • Example 1 Using the apparatus shown in FIG. 2, the amount of molybdenum trioxide (MoO 3 ) deposited on the metal surface was observed.
  • the catalyst cell 22 filled with 800 mg of MoO 3 manufactured by Wako Pure Chemical Industries, Ltd. was sealed so that gas could pass through the outlet 22a of the catalyst cell and MoO 3 particles could not pass. 21 to 500 ° C.
  • the test piece 25 produced by the manufacture example 3 cooled with external air was attached to the exit 22a.
  • Air is introduced into the catalyst cell 22 from the Air feed 23 at a flow rate of 658 ml / hour, liquid water is introduced from the water feed 24 at a flow rate of 0.275 ml / hour to vaporize, and the molybdenum compound released from the outlet 22a is removed.
  • the work of spraying was performed for 20 hours.
  • the test piece 25 to which the sprayed molybdenum compound is attached is taken out, and the attached molybdenum compound is recovered by dissolving it in ammonia water. Quantified with. As a result, the amount of molybdenum adhering to the test piece 25 during 20 hours was 94 micrograms.
  • Example 2 The operation was performed in the same manner as in Example 1 except that the test piece 25 was prepared according to Production Example 4. As a result of measuring the amount of molybdenum attached, the amount of molybdenum attached to the test piece 25 during 20 hours was 9 micrograms.
  • Example 1 The operation was performed in the same manner as in Example 1 except that the test piece 25 was prepared according to Production Example 1. As a result of measuring the amount of molybdenum attached, the amount of molybdenum attached to the test piece 25 during 20 hours was 319 micrograms.
  • Example 2 The operation was performed in the same manner as in Example 1 except that the test piece 25 was prepared according to Production Example 2. As a result of measuring the amount of molybdenum attached, the amount of molybdenum attached to the test piece 25 during 20 hours was 228 micrograms.
  • Example 3 The operation was performed in the same manner as in Example 1 except that the test piece 25 was prepared according to Production Example 5. As a result of measuring the amount of molybdenum attached, the amount of molybdenum attached to the test piece 25 during 20 hours was 304 micrograms.

Abstract

Le but de la présente invention est de réduire efficacement des dépôts d'oxydes de molybdène sur une surface de contact avec laquelle un composé de molybdène libéré à partir d'un catalyseur d'oxyde métallique entre en contact dans un dispositif de réaction en phase gazeuse pour la mise en œuvre d'oxydation en phase gazeuse à l'aide d'un catalyseur d'oxyde qui contient du molybdène. Un dispositif de réaction en phase gazeuse pour la mise en œuvre de réactions à l'aide d'un catalyseur d'oxyde métallique qui contient du molybdène dans lequel la rugosité de surface de la surface de contact avec laquelle un composé de molybdène libéré à partir d'un catalyseur d'oxyde métallique entre en contact est de 0,1 μm à 5 μm inclus et la surface de contact est recouverte d'un film formé par pulvérisation thermique ou placage.
PCT/JP2013/054343 2012-02-22 2013-02-21 Dispositif de réaction en phase gazeuse WO2013125639A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012036315A JP2015086134A (ja) 2012-02-22 2012-02-22 気相反応装置
JP2012-036315 2012-02-22
JP2012-035935 2012-02-22
JP2012035935A JP2015085207A (ja) 2012-02-22 2012-02-22 気相反応装置

Publications (1)

Publication Number Publication Date
WO2013125639A1 true WO2013125639A1 (fr) 2013-08-29

Family

ID=49005816

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/054343 WO2013125639A1 (fr) 2012-02-22 2013-02-21 Dispositif de réaction en phase gazeuse

Country Status (1)

Country Link
WO (1) WO2013125639A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015163260A1 (fr) * 2014-04-25 2015-10-29 三菱レイヨン株式会社 Réacteur à lit fluidisé et procédé de production de composé nitrile au moyen de celui-ci
JP2017512643A (ja) * 2014-03-31 2017-05-25 イネオス ユーロープ アクチェンゲゼルシャフト 酸化又はアンモ酸化反応器用の改良されたエアグリッド設計

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0912612A (ja) * 1995-06-23 1997-01-14 Mitsubishi Chem Corp 塩化ビニル系重合体の製造方法
JP2006247452A (ja) * 2005-03-08 2006-09-21 Daiyanitorikkusu Kk 気相反応装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0912612A (ja) * 1995-06-23 1997-01-14 Mitsubishi Chem Corp 塩化ビニル系重合体の製造方法
JP2006247452A (ja) * 2005-03-08 2006-09-21 Daiyanitorikkusu Kk 気相反応装置

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017512643A (ja) * 2014-03-31 2017-05-25 イネオス ユーロープ アクチェンゲゼルシャフト 酸化又はアンモ酸化反応器用の改良されたエアグリッド設計
WO2015163260A1 (fr) * 2014-04-25 2015-10-29 三菱レイヨン株式会社 Réacteur à lit fluidisé et procédé de production de composé nitrile au moyen de celui-ci
JP2015208705A (ja) * 2014-04-25 2015-11-24 三菱レイヨン株式会社 流動床反応器
KR20160131047A (ko) * 2014-04-25 2016-11-15 미쯔비시 레이온 가부시끼가이샤 유동층 반응기 및 이것을 이용한 니트릴 화합물의 제조 방법
CN106170335A (zh) * 2014-04-25 2016-11-30 三菱丽阳株式会社 流化床反应器及使用其的腈化合物的制造方法
KR20180078333A (ko) * 2014-04-25 2018-07-09 미쯔비시 케미컬 주식회사 유동층 반응기 및 이것을 이용한 니트릴 화합물의 제조 방법
KR101887293B1 (ko) * 2014-04-25 2018-08-09 미쯔비시 케미컬 주식회사 유동층 반응기 및 이것을 이용한 니트릴 화합물의 제조 방법
CN106170335B (zh) * 2014-04-25 2019-05-31 三菱化学株式会社 流化床反应器及使用其的腈化合物的制造方法
KR102005207B1 (ko) * 2014-04-25 2019-07-29 미쯔비시 케미컬 주식회사 유동층 반응기 및 이것을 이용한 니트릴 화합물의 제조 방법

Similar Documents

Publication Publication Date Title
Zhu et al. Preparation of copper-coated β-SiC nanoparticles by electroless plating
JP4673696B2 (ja) 導電性ダイヤモンド電極及びその製造方法
CN101634029B (zh) 8k级镜面效果的不锈钢管内壁表面处理工艺
CN103597118B (zh) 利用硬质膜被覆而成的硬质膜被覆构件及其制造方法
JP5820950B1 (ja) ニッケルめっき液及び固体微粒子付着ワイヤーの製造方法
US20160369405A1 (en) Method and apparatus for preparing coated particles
JP2006247452A (ja) 気相反応装置
WO2013125639A1 (fr) Dispositif de réaction en phase gazeuse
JP5802275B2 (ja) 固体微粒子付着ワイヤー及びその固体微粒子付着ワイヤーの製造方法
JP2004003022A (ja) プラズマ処理容器内部材
Han et al. A smart electroplating approach to fabricate mechanically robust and fluorine-free Ni-W alloys based superhydrophobic coating on Al alloy
CN108264048B (zh) 一种脱除过渡族金属碳化物中游离碳的方法
EP2783025B1 (fr) Procédé d'exfoliation d'une couche de revêtement d'électrode pour électrolyse
JP2015086134A (ja) 気相反応装置
JP6222121B2 (ja) 不溶性電極の製造方法
Manickaraj et al. Malic acid pathway of constructing high-performance Ni anticorrosive coatings using supercritical-CO2 electrodeposition
JP2015085207A (ja) 気相反応装置
CN109609917A (zh) 包括保护装置的管状靶材
CN107892324B (zh) 一种ZnO纳米线阵列的制备方法
CN108203792B (zh) 一种铁基非晶粉末及制备方法
CN110894594A (zh) 一种不锈钢复合材料的石墨烯防腐层的高温涂覆方法
KR20150144018A (ko) 금속계 박막층과 세라믹 코팅층을 포함하는 고온 내식성이 향상된 복합 강판 및 이의 제조방법
JP2011126890A (ja) 気相反応装置
CN110983308A (zh) 一种用于冷凝换热的不锈钢复合材料的制备方法
KR102487913B1 (ko) 비정질 합금 패터닝 방법, 그 방법으로 제조된 비정질 합금 패턴 구조물, 돔 스위치 및 돔 스위치 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13752348

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13752348

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP