CN109071375A - 用于合成腈的方法 - Google Patents
用于合成腈的方法 Download PDFInfo
- Publication number
- CN109071375A CN109071375A CN201780025281.8A CN201780025281A CN109071375A CN 109071375 A CN109071375 A CN 109071375A CN 201780025281 A CN201780025281 A CN 201780025281A CN 109071375 A CN109071375 A CN 109071375A
- Authority
- CN
- China
- Prior art keywords
- coil
- catalyst
- reaction
- induction
- hydrocarbon
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 230000006698 induction Effects 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 23
- 230000005291 magnetic effect Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 230000005307 ferromagnetism Effects 0.000 claims description 5
- 229910017060 Fe Cr Inorganic materials 0.000 claims description 4
- 229910002544 Fe-Cr Inorganic materials 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical group [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 230000005294 ferromagnetic effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229910000953 kanthal Inorganic materials 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000696 magnetic material Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims 2
- 229910000531 Co alloy Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000001282 iso-butane Substances 0.000 claims 1
- 235000013847 iso-butane Nutrition 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical class [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910001006 Constantan Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- -1 ammonia Alkane Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000005303 antiferromagnetism Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005293 ferrimagnetic effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J8/0285—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/18—Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/75—Cobalt
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B6/00—Heating by electric, magnetic or electromagnetic fields
- H05B6/02—Induction heating
- H05B6/10—Induction heating apparatus, other than furnaces, for specific applications
- H05B6/105—Induction heating apparatus, other than furnaces, for specific applications using a susceptor
- H05B6/108—Induction heating apparatus, other than furnaces, for specific applications using a susceptor for heating a fluid
-
- 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
- B01J2208/00433—Controlling the temperature using electromagnetic heating
-
- 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
- B01J2208/00433—Controlling the temperature using electromagnetic heating
- B01J2208/00469—Radiofrequency
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/03—Mononitriles
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种通过氨与烃的吸热催化反应来合成腈的方法，该催化反应使用将交流电流通过金属线圈而获得的热，其中氨与烃之间的吸热反应在反应区具有直接感应加热的反应器中进行。该加热是非常快的，这使得反应实际上瞬间完成。
Description
本发明涉及腈的合成方法。更具体地，本发明涉及通过使用感应加热来合成腈的方法。
腈(例如氰化氢、乙腈、丙烯腈和其他腈，如丙腈和甲基丙烯腈)的非氧化合成是一个高温过程，其发生在700至1000℃。合成这些腈所需的高热量可以以电或感应提供，其优点是，与使用传统加热的方式相比，热更快地供给至反应物进料。
WO 99/01212公开了在固体催化剂存在下感应点燃气相化学反应的方法。具体地，该文献描述了连续流动的气相反应，其中氨与烃在氧和铂族金属催化剂的存在下发生反应，该铂族金属催化剂可由多层铂金属的丝、织物或网组成，以生产氰化氢(HCN)。反应器内的感应线圈用于感应加热金属催化剂并点燃放热反应。
WO 03/078054描述了通过在反应器中的直接感应加热而使氨与甲烷反应来生产HCN的方法。催化剂/感受器是具有各种可能结构的铂族金属或Pt/Rh或Pt/Ir合金，并且反应可以通过围绕催化剂/感受器的感应线圈进行直接加热。
在US 6.315.972中，描述了通过直接感应加热来生产HCN的方法。催化剂包括多个感受器实体泡沫，例如含有催化剂(例如铂族金属或Pt/Rh或Pt/Ir合金)的粒料、环或棒。
在高温下的气相化学反应期间使用感应加热来加热催化剂的构思在本领域中是公知的。因此，US 5.110.996公开了一种方法，其中通过使二氯氟甲烷与甲烷在含有非金属填料和任选的金属催化剂的感应加热的反应管中反应来生产偏二氟乙烯。
类似地，WO 95/21126公开了通过使氨和烃气体在感应加热的石英反应器管中反应来制备HCN。反应器管内的铂族金属催化剂通过螺旋缠绕在石英管外部的感应线圈的存在而被加热，所述线圈由感应电源供电，该感应电源也提供脉冲功率。对于所采用的特定吸热反应，建议使用0.5-30MHz的频率范围以使反应温度保持在600至1200℃。缠绕在反应器管外部的感应线圈本身是金属管，冷却水通过该金属管循环。
通常，感应加热是由磁感应通过涡流(也称为傅科电流，其为由于法拉第(Faraday)感应定律，由导体内的变化磁场在导体内感应的电流回路)和/或磁滞损耗在物体中产生的热量加热导电物体(通常是金属)的过程。涡流在垂直于磁场的平面中在导体内以闭环中流动。
感应加热器由电磁铁和电子振荡器组成，其使高频交流电(AC)通过电磁铁。快速交变的磁场穿透物体，由此在导体内部产生称为涡流的电流。流过材料电阻的涡流将通过Joule(焦耳)加热来使其加热。涡流加热也表示为欧姆加热。在诸如铁的铁磁性(和亚铁磁性和反铁磁性)材料中，可替代地或另外地可通过磁滞损耗产生热量。这表示为铁磁加热。所用电流的频率取决于物体尺寸、材料类型、耦合(感应线圈和待加热物体之间)和穿透深度。包括弯曲成多个环型或绕组形式的导体的感应线圈是电磁铁的一个实例。
加热铁磁性材料比加热非铁磁性材料相对更快和更便宜。铁磁性材料具有固有或本征最高加热温度，即居里温度。因此，使用铁磁性催化剂材料确保吸热化学反应不会被加热至超过特定温度，即居里温度。因此，确保了化学反应不会失控。
感应加热通常使用通过线圈的通常为高频的交流电进行。待加热的物体置于线圈内。然而，该过程不是非常能量有效的，因为线圈产生的磁场也将在线圈外部继续。虽然可通过将线圈成形为环面来避免这个缺点，但是由于线圈中的电阻，即欧姆热(其通常会在该过程中损失)，仍然会有损耗。
现在已经证明，有可能建立一种更加能量有效的方法。在所述方法中，线圈将安装在反应器内，催化剂将置于线圈内。这样，该过程不会损失欧姆热，并且如果压力壳基于具有低磁滞的铁，或者可替代地，压力壳内部涂敷有这种铁类型，由线圈产生的磁场将不能穿透反应器。在非常高的温度下，可封闭反应器并可能通过使温度保持低于居里(Curie)温度来对其实施保护，该居里温度是这样的温度，其中某些材料在该温度下失去其永久磁性且被感应磁性替代。通常，线圈可以由耐受还原性气体的Kanthal型(Fe-Cr-Al合金)线制成。线圈也可以由铜线；康铜线；由铁-铬-铝(FeCrAl)合金、铜和锰及镍的合金及其组合制成的线制成。优选地，线圈由Kanthal型线制成。
可以放置线圈，使其与催化剂直接电接触。在这种情况下，将发生催化剂的额外欧姆加热。此外，不需要线圈的电绝缘。
因此，本发明涉及一种通过氨与烃的催化反应来合成腈的方法，该催化反应使用将交流电流通过金属线圈而获得的热，其中氨与烃之间的吸热反应通过反应区中的直接感应加热进行。
感应加热使得能够以大于70W/g的热功率进行加热，其给出大于150℃/s的加热速率。因此，感应加热提供了一种非常快速和有效的加热方式。这在图1中示出，图2示出了经受磁场变化的Fe-Cr和Al-Ni-Co合金的温度如何随时间而变化。
在铁磁性结构和合适涂层的可能组合中，发现最好的情况是由金属Fe-Cr或Al-Ni-Co合金组成的结构。
Fe-Cr合金具有约为560℃的居里温度，该温度是某些材料失去其永久磁性的温度。涂层是基于氧化物的，其可以是由Al、Zr、Ce等组合而制成的氧化物。
涂覆的金属结构具有多孔的氧化物表面，其可以用实际上任何催化相浸渍。因此，它可以与任何用于腈合成的常规催化剂，例如基于Co和Sn的催化剂匹配。
以这种方式可能难以获得足够活性。因此，另一种可能性是用磁性材料稀释常规催化剂。
由于热是从反应器内部供应，这使得催化剂成为反应器中最热的部分，因此反应不需要庞大且昂贵的加热设备。极快的加热使反应实际上瞬间完成。
在本发明范围内，氨和烃之间的代表性反应包括以下：
CH4+NH3<->HCN(氰化氢)+3H2
C2H6+NH3<->CH3CN(乙腈)+3H2
C3H8+NH3<->C2H3CN(丙烯腈)+4H2
C3H8+NH3<->C2H5CN(丙腈)+3H2
异-C4H10+NH3<->异-C3H5CN(甲基丙烯腈)+4H2
需要600至900℃的温度以克服平衡限制，因为反应是高度吸热的。
合成这些腈所需的高热量可以以电加热或感应加热提供。至关重要的是，为这些反应快速提供热量以使热碳沉积最小化。感应加热还向催化剂颗粒提供更有效的热传递，这与使用外部加热的反应器壁介质获得的(其导致热损失)不同。
在反应器设计中，可以再次有效地使用不同的具有最小传热损失的加热区。由于反应是高度吸热的，因此可以通过调节反应器不同部分的等温条件来改善整个反应器的转化曲线。
可以使用双金属催化剂，其还可以使用铁磁性材料以为这些反应提供加热。即使在双金属催化剂不是铁磁性的情况下，它们也可以与待与感应加热一起使用的铁磁性材料混合或被铁磁性材料包围。
在下面的实施例中进一步说明本发明。
实施例
腈合成在低压下进行。使用烷烃或烯烃与氨的混合物，可能还有载气如氮气或甲烷。通过热交换将气体混合物加热至450-550℃，然后其进入经感应加热的反应区。
如果可能的话，感应加热器由具有高的电矫顽力的铁磁性催化剂(铁磁性材料承受外部电场而不成为去极化的能力)组成。或者，催化剂可以与具有高的矫顽力的铁磁性材料混合。该材料对于反应混合物中的气体应呈惰性。
反应在600至800℃的反应器温度下进行，并且在离开反应器后，流出物气体在进料/流出物热交换器中被冷却至低于200℃的温度。分离所需产物，同时将未转化的烃混合到补充气体中。
Claims (10)
1.一种通过氨与烃的催化反应来合成腈的方法，所述催化反应使用将交流电流通过金属线圈而获得的热，其中氨与烃之间的吸热反应在反应区具有直接感应加热的反应器中进行。
2.根据权利要求1所述的方法，其中所述线圈安装在合成反应器内，并且所述催化剂放置在所述线圈内。
3.根据权利要求1或2所述的方法，其中所述线圈由Kanthal型(Fe-Cr-Al合金)线制成。
4.根据权利要求1或2所述的方法，其中通过使用感应加热器进行感应加热，所述感应加热器是设置有合适涂层的铁磁性金属结构，并且其中通过磁滞损耗产生热。
5.根据权利要求4所述的方法，其中所述感应加热器由具有高的电矫顽力的铁磁性催化剂组成。
6.根据权利要求5所述的方法，其中所述催化剂用磁性材料稀释。
7.根据权利要求1至4中任一项所述的方法，其中所述金属结构是选自Fe-Cr和Al-Ni-Co合金的金属。
8.根据权利要求7所述的方法，其中所述金属结构涂覆有多孔氧化物表面，所述多孔氧化物表面用催化相浸渍。
9.根据权利要求8所述的方法，其中所述催化相含有基于Co或Sn的催化剂。
10.根据前述权利要求中任一项所述的方法，其中所述烃是甲烷、乙烷、丙烷、异丁烷和烯烃。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201600246 | 2016-04-26 | ||
| DKPA201600246 | 2016-04-26 | ||
| PCT/EP2017/059598 WO2017186615A1 (en) | 2016-04-26 | 2017-04-24 | A process for the synthesis of nitriles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109071375A true CN109071375A (zh) | 2018-12-21 |
Family
ID=58609413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780025281.8A Pending CN109071375A (zh) | 2016-04-26 | 2017-04-24 | 用于合成腈的方法 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US11319284B2 (zh) |
| EP (1) | EP3448833A1 (zh) |
| JP (1) | JP7050695B2 (zh) |
| CN (1) | CN109071375A (zh) |
| WO (1) | WO2017186615A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114667187A (zh) * | 2019-09-19 | 2022-06-24 | 国立图卢兹应用科学学院 | 包含微米铁磁材料的催化组件以及所述组件用于多相催化反应的用途 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3574991A1 (en) | 2018-05-31 | 2019-12-04 | Haldor Topsøe A/S | Steam reforming heated by resistance heating |
| FR3100988B1 (fr) * | 2019-09-19 | 2023-03-10 | Institut Nat Des Sciences Appliquees De Toulouse | Procédé de catalyse hétérogène mettant en œuvre un matériau ferromagnétique chauffé par induction magnétique et support de catalyseur utilisé pour ledit procédé |
| CA3148730A1 (en) * | 2019-10-01 | 2021-04-08 | Haldor Topsoe A/S | Cyanide on demand |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687658A (zh) * | 2007-05-14 | 2010-03-31 | 因温斯特技术公司 | 高效反应器和方法 |
| DK201500118A1 (en) * | 2015-03-02 | 2015-03-23 | Haldor Topsøe As | Catalyst for induction heated high temperature endothermic reaction |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948645A (en) | 1973-04-30 | 1976-04-06 | Boliden Aktiebolag | Method of carrying out heat-requiring chemical and/or physical processes in a fluidized bed |
| GB8722847D0 (en) | 1987-09-29 | 1987-11-04 | Electricity Council | Performing endothermic catalytic reactions |
| GB8724561D0 (en) | 1987-10-20 | 1987-11-25 | Ici Plc | Production process |
| US6315972B1 (en) * | 1994-02-01 | 2001-11-13 | E.I. Du Pont De Nemours And Company | Gas phase catalyzed reactions |
| WO1995021126A1 (en) | 1994-02-01 | 1995-08-10 | E.I. Du Pont De Nemours And Company | Preparation of hydrogen cyanide |
| US5958273A (en) * | 1994-02-01 | 1999-09-28 | E. I. Du Pont De Nemours And Company | Induction heated reactor apparatus |
| WO1996015983A1 (en) | 1994-11-24 | 1996-05-30 | Quadro Chemicals (Proprietary) Limited | Hydrogen cyanide gas production |
| CN1112961C (zh) * | 1997-07-03 | 2003-07-02 | 纳幕尔杜邦公司 | 感应加热的催化反应器 |
| US7070743B2 (en) * | 2002-03-14 | 2006-07-04 | Invista North America S.A R.L. | Induction-heated reactors for gas phase catalyzed reactions |
| FR3003774B1 (fr) | 2013-04-02 | 2018-03-02 | Institut National Des Sciences Appliquees De Toulouse | Procede chimique catalyse par des nanoparticules ferromagnetiques |
| US11059719B2 (en) | 2016-04-26 | 2021-07-13 | Haldor Topsøe A/S | Process for producing hydrogen or syngas by methanol cracking |
-
2017
- 2017-04-24 CN CN201780025281.8A patent/CN109071375A/zh active Pending
- 2017-04-24 EP EP17718915.6A patent/EP3448833A1/en active Pending
- 2017-04-24 JP JP2018555931A patent/JP7050695B2/ja active Active
- 2017-04-24 WO PCT/EP2017/059598 patent/WO2017186615A1/en active Application Filing
- 2017-04-24 US US16/096,493 patent/US11319284B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687658A (zh) * | 2007-05-14 | 2010-03-31 | 因温斯特技术公司 | 高效反应器和方法 |
| DK201500118A1 (en) * | 2015-03-02 | 2015-03-23 | Haldor Topsøe As | Catalyst for induction heated high temperature endothermic reaction |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114667187A (zh) * | 2019-09-19 | 2022-06-24 | 国立图卢兹应用科学学院 | 包含微米铁磁材料的催化组件以及所述组件用于多相催化反应的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017186615A9 (en) | 2018-12-13 |
| US20190144376A1 (en) | 2019-05-16 |
| US11319284B2 (en) | 2022-05-03 |
| WO2017186615A1 (en) | 2017-11-02 |
| JP7050695B2 (ja) | 2022-04-08 |
| EP3448833A1 (en) | 2019-03-06 |
| JP2019514901A (ja) | 2019-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109071249B (zh) | 用于氨合成转化器的启动加热的方法 | |
| CN109071375A (zh) | 用于合成腈的方法 | |
| TWI275415B (en) | Induction-heated reactors for gas phase catalyzed reactions | |
| US11059010B2 (en) | Induction heated reactor | |
| CN108136353A (zh) | 烷烃的脱氢 | |
| US11059719B2 (en) | Process for producing hydrogen or syngas by methanol cracking | |
| EP3448803B1 (en) | Ammonia dissociation by use of inductive heating | |
| US10207241B2 (en) | Inductively heated microchannel reactor | |
| EA041820B1 (ru) | Способ нагрева при пуске реактора конверсии в установке синтеза аммиака |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |