WO2012143330A1 - Procédé de préparation d'une hydroxylamine - Google Patents

Procédé de préparation d'une hydroxylamine Download PDF

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Publication number
WO2012143330A1
WO2012143330A1 PCT/EP2012/056923 EP2012056923W WO2012143330A1 WO 2012143330 A1 WO2012143330 A1 WO 2012143330A1 EP 2012056923 W EP2012056923 W EP 2012056923W WO 2012143330 A1 WO2012143330 A1 WO 2012143330A1
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WIPO (PCT)
Prior art keywords
nitrate
range
hydroxylamine
reaction zone
mol
Prior art date
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PCT/EP2012/056923
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English (en)
Inventor
Marijke Hilde Leen GROOTHAERT
Johan Thomas Tinge
Rudolph Philippus Maria Guit
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Dsm Ip Assets B.V.
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Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Priority to KR1020137027597A priority Critical patent/KR101904568B1/ko
Priority to CN201280019822.3A priority patent/CN103492312B/zh
Publication of WO2012143330A1 publication Critical patent/WO2012143330A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/14—Hydroxylamine; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/14—Hydroxylamine; Salts thereof
    • C01B21/1409—Preparation
    • C01B21/1418—Preparation by catalytic reduction of nitrogen oxides or nitrates with hydrogen
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
    • C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other 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
    • B01J23/38—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to a method for preparing hydroxylamine in a continuous process, to a method for preparing oximes, and to a method for preparing lactams.
  • ⁇ Hydroxylamine
  • caprolactam are generally known in the art, e.g. from Ullmann's Encyclopedia of Industrial Chemistry, for instance the 7 th edition (2005), Chapter on Caprolactam (DOI: 10.1002/14356007. a05.031 (Retrieved Feb. 18, 201 1).
  • Other oximes of which the preparation using hydroxylamine has been described include cyclodedocecanone oxime (e.g. EP-A 1 ,329, 448) and butanone oxime.
  • a05.031 (Retrieved Feb. 18, 2011) makes use of two recycling liquids - an inorganic liquid and an organic liquid - in which several reactions and operations take place.
  • Gaseous hydrogen is contacted, in a gas-liquid reactor, with a circulating inorganic liquid containing nitrate ions, together with a buffering acid and the catalyst.
  • the hydrogen containing gas phase is circulated over the bubble column type reactor by a circulation compressor.
  • Fresh hydrogen is fed to the circulation gas, a small amount being withdrawn from the system to maintain a constant hydrogen pressure.
  • Inert gaseous components in the fresh hydrogen and the produced gaseous by-products N 2 and N 2 0 are removed via the gas purge.
  • the gas-liquid suspension is circulated by the Mammoth pump principle from the gassed reactor section, over gas-liquid separators, to the filter candles in the filtration section and via a heat exchanger for the removal of heat of reaction, back to the gassed reactor section.
  • the inorganic liquid obtained after filtration is then contacted in the oximation section with an organic liquid, being a mixture of toluene and cyclohexanone.
  • cyclohexanone is practically quantitatively converted into cyclohexanone oxime.
  • the obtained cyclohexanone oxime-containing organic phase is distilled to recover the toluene.
  • the inorganic liquid leaving the oximation section has to be purified thoroughly to protect the catalyst in the hydroxylamine reactor. This is done by extraction with toluene, followed by stripping with steam. In the stripping column the water that is co-produced during the preparation of hydroxylamine and cyclohexanone oxime is also removed. A small amount of ammonia by-product remains in solution, but is prevented from building up by conversion of ammonia into nitrogen in an absorber for a gas mixture of NO and N0 2 (i.e. of nitric oxide and nitrogen dioxide; hereinafter also referred to as nitrous gases).
  • NO and N0 2 i.e. of nitric oxide and nitrogen dioxide
  • EP1947056A1 describes a method for preparing hydroxylamine by reduction of nitrate with hydrogen gas in the presence of a catalyst in an inorganic process solution containing an acidic buffering agent, as part of a combined
  • US2006/0079678A1 describes a process for preparing hydroxylammonium by catalytic reduction of nitrate or nitrogen oxide with hydrogen, as part of a system of producing cyclohexanone oxime. It teaches an improved distillation of the cyclohexanone oxime product stream, involving recycle to the cyclohexanone oxime synthesis zone of cyclohexanone distilled therefrom.
  • concentration of hydroxylamine is, for instance, reducing the liquid residence time, in combination with an increased catalyst concentration and/or an increased temperature and/or an increased hydrogen partial pressure. At some point it is not possible anymore to further increase the liquid feed rate without need for high investments in other parts of the loop.
  • hydroxylamine conversion is obtained in its reaction with cyclohexanone in the downstream oximation reaction step.
  • carbonyls which act as a poison for the catalyst
  • crystallization temperature crystals will form. If this occurs on the surface of the reactor where cooling occurs, the crystal will insulate the reaction from cooling, and a loss of process control will occur. This could easily accelerate to severe fouling and a need to stop the reactor for cleaning; a severe disruption.
  • the crystallization temperature of the reaction mixture should ideally remain higher than the temperature of the cooling water used to remove the heat of the hydrogenation reaction. This limits the maximum hydroxylamine product concentration at which the nitrate hydrogenation reactor can be operated.
  • the present invention relates to a method for preparing hydroxylamine in a continuous process, comprising feeding nitrate and phosphate in an acidic aqueous liquid into a reaction zone and reducing nitrate with hydrogen thereby forming hydroxylamine, wherein the feed of nitrate and phosphate, the hydrogen and the temperature are controlled such that the nitrate concentration in the reaction zone is less than 1.0 mol/kg, as determined in liquid leaving the reaction zone; the molar ratio of nitrate to phosphate in the reaction zone is 0.5 or less; and the molar ratio of ammonia to nitrate is in the range of from 2.2 to 7.
  • the reduction of nitrate is generally a catalysed reaction.
  • nitrate concentration in the reaction zone less than 1.0 mol/kg, as determined in the liquid leaving the reaction zone; molar ratio of nitrate to phosphate in the reaction zone of 0.5 or less; and molar ratio of ammonia to nitrate in the range of from 2.2 to 7, lead to reaction mixtures having particularly low crystallization temperatures, but which retain high conversion to hydroxylamine.
  • the present invention surprisingly provides a way to prepare hydroxylamine at an advantageous production capacity, with a reduced risk of fouling due to crystallization of substances in the reaction zone.
  • hydroxylamine in a reaction liquid in a concentration of 1.2 mol/kg or more; preferably 1.3 or more, more preferably 1.4 or more, or 1.5 or more.
  • a high hydroxylamine concentration is advantageous because the reaction system is thus intensified and productivity is improved.
  • the hydroxylamine concentration is 2 mol/kg or less, in particular 1.9 mol/kg or less, more in particular 1.8 mol/kg liquid reaction product or less.
  • a method according to the invention is advantageous in that less catalyst may be needed per produced quantity of hydroxylamine in order to realise a specific production capacity.
  • a method according to the invention is advantageous with respect to the further use of hydroxylamine in the preparation of an oxime, such as cyclohexanone oxime.
  • the hydroxylamine usually leaves the reaction zone in a product reaction mixture, which typically is an aqueous liquid comprising the hydroxylamine, phosphate, any unreacted nitrate, and ammonia.
  • the reaction product mixture from the hydroxylamine preparation is found to be particularly suitable as a feed for a method for preparing an oxime, the advantage residing in a more effective oximation reaction and/or oxime extraction from the oximation reaction product mixture,.
  • the preparation of hydroxylamine can suitably be carried out in a known continuous reactor for preparing hydroxylamine.
  • the reaction is carried out in a reactor providing well mixed gas/liquid systems.
  • Such systems are well-known in the art and include stirred tank reactors, internal loop reactors, external loop reactors, and bubble column reactors.
  • a bubble column reactor is used. Good results have in particular been achieved using a bubble column reactor with external gas-lift.
  • the concentration of the substance or a concentration derived parameter (such as a ratio of concentrations of substances) in the reaction zone can be determined by determining that parameter in a sample taken from the process liquid leaving the reaction zone.
  • the nitrate concentration in the reaction zone is less than 1.0 mol/kg, as determined in the liquid leaving the reaction zone.
  • the nitrate concentration is 0.9 mol/kg or less, in particular 0.8 mol/kg or less. Particularly good results have been achieved with a nitrate concentration of about 0.70 or less.
  • the nitrate concentration is at least 0.3 mol/kg, in particular at least 0.4 mol/kg.
  • the nitrate concentration is at least 0.45 mol/kg, more preferably at least 0.50 mol/kg.
  • the molar ratio of ammonia to nitrate is in the range of from 2.2 to 7.
  • a molar ratio of 6 or less, in particular of 5 or less, is particularly preferred for a high productivity. It is in particular contemplated that this is advantageous for a high catalytic activity of the catalyst, with respect to catalysing the reduction of nitrate to form hydroxylamine.
  • a molar ratio of ammonia to nitrate of 2.3 or more, in particular of 2.4 or more or of 2.5 or more is particularly preferred for a low fouling tendency.
  • a molar ratio in the range of from 2.3 to 6, more preferably of from 2.4 to 5, or most preferably of from 2.5 to 5 is advantageous for a high catalytic activity of the catalyst, with respect to catalysing the reduction of nitrate to form hydroxylamine.
  • the phosphate is usually provided as phosphoric acid or a hydrogen phosphate salt (which may be formed by adjusting the pH of a phosphoric acid solution with an appropriate base, such as a hydroxide or ammonia).
  • the molar ratio of nitrate to phosphate usually is at least 0.05, preferably at least 0.10. Excellent results are achieved at values of at least 0.15, more in particular of at least 0.20.
  • the molar ratio of nitrate to phosphate preferably is 0.40 or less, in particular 0.35 or less, more in particular 0.30 or less.
  • Hydrogen can be fed into the reaction zone in a manner and at a concentration (hydrogen pressure) known per se.
  • the pressure is at least approx. 0.5 MPa, more preferably at least approx. 1.0 MPa.
  • the hydrogen pressure is 10 MPa or less.
  • the buffer ratio is chosen within a specific range.
  • the buffer ratio is defined as: ([H + ] + [HYAM])/[phosphate] wherein:
  • [H + ] molar concentration of H + in mol/kg in the aqueous liquid leaving the reaction zone.
  • [phosphate] total concentration of phosphate (including phosphate in H 3 P0 4 ,
  • [H+], [HYAM] and [phosphate] concentrations are all determined by equilibrium titration of one sample, by subsequently titrating a sample of the liquid from the reaction zone at 25 °C with 0.25 N aqueous NaOH solution) to get the [H + ] concentration ("free acid") at the first equilibrium point (at a pH of about 4.2); next molar excess of acetone is added to the sample, to convert hydroxylamine into an oxime and H + , and equilibrium titration is continued so as to subsequently reach three further equivalence points, the first of which is corresponding to the free acid coming from hydroxylamine (and thus provides the value for [HYAM] in the sample); the second of which provides the value for [phosphate], and the last of which provides a value for ammonium. The latter value, however, is not needed here.
  • the buffer ratio preferably is in the range of from 0.4 to 0.8, in particular in the range of from 0.45 to 0.70, more in particular in the range of from 0.50 to 0.65 mol/mol.
  • the molar H + concentration during the reaction is usually in the range of from 0.4 to 0.8 mol/kg, in particular in the range of from 0.45 to 0.70 mol/kg, more in particular in the range of from 0.50 to 0.65 mol/kg.
  • the preparation of hydroxylamine in accordance with the invention is in general catalysed by a metal catalyst.
  • Suitable catalysts are generally known in the art.
  • a catalyst comprising palladium may be used.
  • the catalyst may comprise one or more (catalytic) metals, in particular palladium.
  • the catalyst is usually provided on a carrier.
  • good results have been achieved with a catalyst comprising palladium on carbon.
  • the catalyst is provided with a promoter for the catalyst, such as germanium oxide. The promoter can be added at any time during the method of preparing hydroxylamine, as desired.
  • the temperature may in particular be in the range of from 20 to 70 °C, preferably in the range of from 30 to 60 °C, in particular in the range of from 35 to 55 °C.
  • the hydroxylamine prepared in accordance with the invention may be recovered from the reaction product mixture obtained in the reaction zone by a conventional technique, or the reaction product mixture may be fed into a further process, such as into a method for preparing an oxime (optionally after it has been treated, e.g. to remove one or more undesired components).
  • the invention also relates to the use of hydroxylamine obtained in a method according to the invention for the preparation of an oxime.
  • the oxime may be prepared from the hydroxylamine in a manner know per se.
  • the method typically comprises reacting hydroxylamine obtained in a method according to the invention with an alkanone.
  • the alkanone may be cyclic or non-cyclic.
  • Preferred cycloalkanones are cyclohexanone, to obtain cyclohexanone oxime, and cyclododecahexanone, to obtain cyclododecanone oxime.
  • Butanone is a preferred non-cyclic alkanone; butanone oxime is then prepared.
  • the invention is further directed to a method for preparing cyclohexanone oxime, comprising hydroxylamine obtained in a method according to the invention with cyclohexanone.
  • This method may be carried out in a manner known per se, e.g. as described in the above identified prior art, of which the contents are incorporated herein by reference with respect to suitable conditions.
  • a (cyclic) oxime obtained in accordance with the invention may in particular be used for preparing a lactam. This can be accomplished by Beckmann rearrangement, in a manner known per se.
  • cyclohexanone oxime obtained in accordance with the invention may be used in the preparation of caprolactam.
  • the invention is further directed to a method for preparing caprolactam, comprising subjecting cyclohexanone oxime, obtained in a method according to the invention to Beckmann rearrangement, thereby forming caprolactam.
  • the preparation of caprolactam may be carried out in a manner known per se, e.g. as described in the above identified prior art, of which the contents are incorporated herein by reference with respect to suitable conditions.
  • laurolactam is obtained in an embodiment of the invention by a method comprising subjecting cyclododecanone oxime, obtained in accordance with the invention, to Beckmann rearrangement, thereby forming laurolactam.
  • This preparation step may also be carried out in a manner known per se.
  • the method for preparing a (cyclic) oxime, such as cyclohexanone oxime, and - if desired - the method for making a lactam there from, such as caprolactam, are usually integrated in a single plant wherein hydroxylamine, oxime and - if desired - lactam are prepared in a continuous process.
  • the nitrate reduction was carried out in an industrial gas lift loop reactor consisting of a gassed riser section, a liquid-gas separation section, a gas recycle section, a filtration section to separate part of the circulating liquid as product (wherein concentrations shown in Table 1 were determined; these correspond to the concentrations in the reaction zone) from the catalyst-containing reactor liquid.
  • Fresh hydrogen was fed to the reactor and a gas purge was applied such that the hydrogen partial pressure was maintained at approx. 1.4 MPa in the top section of the reactor.
  • the average reactor temperature was maintained at approx. 50 °C.
  • As catalyst 10 wt% Pd/C was used.
  • As activator approx. 45 gram Ge0 2 per kg Pd was added.
  • the catalyst (as dry Pd/C) concentration based on the inorganic process liquid present in the reactor was approx. 1 wt%.
  • Feeding rate and feed composition of the inorganic process liquid fed to the reactor were varied in wide ranges as shown in Table 1 , resulting in different composition of the reactor product and hydroxylamine production rate.
  • Table 1 both data for the performance of the nitrate reduction reactor under reference conditions ('Plant ref.') and data for the performance of the nitrate reduction reactor in the process according to the invention in which nitrate concentration and nitrate to phosphate ratios have been reduced ( ⁇ 1' up to and including ⁇ 5'), in combination with increased values for ammonia versus nitrate ratios, are shown.
  • the activity in Table 1 is based on the amount of catalyst (as dry Pd/C) present in the gassed riser zone of the hydrogenation reactor.
  • the inorganic liquid product composition as exemplified in Table 1 ⁇ 1' up to and including ⁇ 5', may be compared with the composition of the inorganic liquid product as obtained in 7 experiments given in US-6,759,556 (for which crystallization temperatures were determined by the present inventors) and which are shown in Table 2.
  • Table 1 Plant experiments at reference conditions and at reduced nitrate and nitrate to phosphate ratios.
  • Table 2 Liquid composition of the nitrate reduction reactor for high hydroxylamine concentrations according to US-6,759,556.
  • Product mixtures were prepared to simulate the effect of product concentration on the resulting crystallization point of the product mixture.
  • the composition of the product mixture was adjusted for key performance numbers like H + and buffer ratio at desired levels and N0 3 " concentration was at a level at which high reaction rates would be expected by a person of ordinary skill in the art.
  • Table 3 shows in an otherwise conventional process window, but now at relatively high N0 3 " concentrations, relatively high N0 3 " to phosphate ratios and at relatively low NH 4 + to N0 3 " ratios, that the crystallization temperatures of the product mixture increase at an increasing hydroxylamine product concentration, as compared to the results as shown in Table 1.
  • crystallization temperatures preferably should be controlled below 25 °C and in particular below 20 °C.
  • Table 3 demonstrate that operating at high hydroxylamine concentrations generally leads to an increased risk of crystallization under conditions at a level at which high reaction rates would be expected by a person of ordinary skill in the art.
  • Table 3 Example of the effect of increased hydroxylamine product concentration on the crystallization temperature of the product mixture in the process window of NH 4 + /N0 3 " ⁇ 2.2 mol/mol

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

Abstract

La présente invention concerne un procédé de préparation d'une hydroxylamine au cours d'un procédé continu, comprenant l'alimentation d'une zone de réaction en nitrates et en phosphates présents dans un liquide aqueux acide et la réduction des nitrates par de l'hydrogène formant ainsi l'hydroxylamine, la concentration en nitrates dans la zone de réaction, telle que déterminée dans le liquide quittant la zone de réaction, étant inférieure à 1,0 mol/kg, le rapport molaire nitrates sur phosphates dans la zone de réaction étant inférieur à 0,5, et le rapport molaire ammoniac sur nitrates étant situé dans la plage allant de 2,2 à 7. L'invention concerne également un procédé de préparation d'une oxime et un procédé de préparation d'un lactame comprenant ledit procédé de préparation d'une hydroxylamine.
PCT/EP2012/056923 2011-04-22 2012-04-16 Procédé de préparation d'une hydroxylamine WO2012143330A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020137027597A KR101904568B1 (ko) 2011-04-22 2012-04-16 하이드록실아민의 제조 방법
CN201280019822.3A CN103492312B (zh) 2011-04-22 2012-04-16 制备羟胺的方法

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Application Number Priority Date Filing Date Title
EP11163580.1 2011-04-22
EP11163580 2011-04-22

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CN115092897A (zh) * 2022-07-21 2022-09-23 河北工业大学 一种乙烯基改性二氧化硅接枝酸性聚合离子液体催化环己酮肟水解制备羟胺的方法

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CN109836353A (zh) * 2017-11-27 2019-06-04 黄飞熊 优化制造环己酮肟的方法
CN113735076A (zh) * 2021-09-14 2021-12-03 宁波四明化工有限公司 一种制备羟胺盐的方法

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GB1287303A (en) 1968-11-12 1972-08-31 Stamicarbon Preparation of oxime
US5364609A (en) 1992-06-16 1994-11-15 Dsm N.V. Process for the preparation and processing of a hydroxylammonium salt solution
US5792439A (en) * 1995-11-10 1998-08-11 Dsm N.V. Process for the preparation of hydroxylammonium salts
EP1329448A1 (fr) 2002-01-16 2003-07-23 Ube Industries, Ltd. Procédé de préparation de laurolactame à partir de cyclododécanone
US6759556B2 (en) 2000-06-05 2004-07-06 Dsm N.V. Process for the production of cyclohexanone oxime
US20060079678A1 (en) 2003-01-30 2006-04-13 Hendrik Oevering Process for treating an organic solution comprising cyclohexanone oxime, cyclohexanone, an orgainc solvent
EP1947056A1 (fr) 2007-01-05 2008-07-23 China Petrochemical Development Corporation Système de recyclage pour la formation et d'oxydation d'hydroxylamine
EP1303480B1 (fr) 2000-06-05 2009-03-18 DSM IP Assets B.V. Procede de production de cyclohexanone oxime

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KR101311626B1 (ko) * 2005-07-08 2013-09-26 디에스엠 아이피 어셋츠 비.브이. 하이드록실 암모늄의 연속 제조 방법

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Publication number Priority date Publication date Assignee Title
GB1287303A (en) 1968-11-12 1972-08-31 Stamicarbon Preparation of oxime
US5364609A (en) 1992-06-16 1994-11-15 Dsm N.V. Process for the preparation and processing of a hydroxylammonium salt solution
US5792439A (en) * 1995-11-10 1998-08-11 Dsm N.V. Process for the preparation of hydroxylammonium salts
US6759556B2 (en) 2000-06-05 2004-07-06 Dsm N.V. Process for the production of cyclohexanone oxime
EP1303480B1 (fr) 2000-06-05 2009-03-18 DSM IP Assets B.V. Procede de production de cyclohexanone oxime
EP1329448A1 (fr) 2002-01-16 2003-07-23 Ube Industries, Ltd. Procédé de préparation de laurolactame à partir de cyclododécanone
US20060079678A1 (en) 2003-01-30 2006-04-13 Hendrik Oevering Process for treating an organic solution comprising cyclohexanone oxime, cyclohexanone, an orgainc solvent
EP1947056A1 (fr) 2007-01-05 2008-07-23 China Petrochemical Development Corporation Système de recyclage pour la formation et d'oxydation d'hydroxylamine

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"Ullmann's encyclopedia of industrial chemistry", 2005, pages: 6,7
H.J. DAMME; J.T. VAN GOOLEN; A.H. DE ROOIJ: "Cyclohexanone oxime made without by-product (NH4)2S04", CHEMICAL ENGINEERING, 10 July 1972 (1972-07-10), pages 54,55

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115092897A (zh) * 2022-07-21 2022-09-23 河北工业大学 一种乙烯基改性二氧化硅接枝酸性聚合离子液体催化环己酮肟水解制备羟胺的方法

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KR101904568B1 (ko) 2018-10-04
TW201247527A (en) 2012-12-01
CN103492312B (zh) 2016-11-02
CN103492312A (zh) 2014-01-01

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