WO2020078884A1 - Processus et installation améliorés pour la production d'oximes - Google Patents

Processus et installation améliorés pour la production d'oximes Download PDF

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WO2020078884A1
WO2020078884A1 PCT/EP2019/077744 EP2019077744W WO2020078884A1 WO 2020078884 A1 WO2020078884 A1 WO 2020078884A1 EP 2019077744 W EP2019077744 W EP 2019077744W WO 2020078884 A1 WO2020078884 A1 WO 2020078884A1
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oxime
aqueous phase
cyclohexanone
phosphate
section
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Johannes OP HET VELD
Marijke Hilde Leen GROOTHAERT
Johann Thomas TINGE
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Cap III BV
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Cap III BV
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    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring

Definitions

  • the present invention relates to a process and a plant for the removal of phosphate from wastewater originating from the production of oximes.
  • Oximes are usually generated by the reaction of hydroxylamine and aldehydes or ketones.
  • Examples of oximes are butanone oxime, cyclohexanone oxime and cyclododecanone oxime that are made by condensation of hydroxylamine and butanone, cyclohexanone, and cyclododecanone, respectively.
  • Butanone oxime also called methylethyl ketone oxime
  • Cyclododecanone oxime is mainly consumed as a precursor to laurolactam, which is a precursor of polyamide-12 (also known as nylon-12).
  • Cyclohexanone oxime is an intermediate in the production of, amongst other compounds, caprolactam. This monomer is commonly used in the production of polyamide-6 (also known as nylon-6).
  • a process for the production of oximes is based on the selective reaction of cyclohexanone, ammonia, and hydrogen peroxide in the presence of a catalyst.
  • titanium silicalite based catalysts are very suitable for this so- called ammoximation reaction.
  • Methods for the production of such catalysts are known in the art (see for example, US 4,410,501 and US 9,896,343).
  • Catalytic processes for the manufacture of cyclohexanone oxime by ammoximation in the liquid phase of cyclohexanone with NH 3 and H 2 0 2 are also known in the art (see for example, US 4,794,198, EP 1 674 448 and US 7,408,080).
  • the formed cyclohexanone oxime is purified and recovered by extraction, (caustic) aqueous washing and distillation steps.
  • Oxime production processes based on ammoximation produce large amounts of wastewater containing significant amounts of organic and inorganic components.
  • the main source of water is diluent water stemming from the raw materials (e.g., aqueous hydrogen peroxide) and water that is chemically formed in the ammoximation process (see e.g., Reaction 1 ).
  • a typical cyclohexanone ammoximation process produces at least 2.5 tons of wastewater per ton of produced cyclohexanone oxime. Typically, this wastewater is discharged to a biochemical wastewater treatment plant.
  • CN 103 214 044, CN 101 618 919 and CN 101 734 825 describe methods to oxidize the organic material in the wastewater of an ammoximation plant, so as to improve the biodegradability, before it is charged to a biochemical wastewater treatment plant.
  • removal of phosphorus, that might be present in inorganic form, e.g., in the form of phosphate, or in organic form, e.g., in the form of trioctyl phosphate from wastewater of an ammoximation plant has, to the knowledge of the inventors, never been disclosed in the prior art.
  • the phosphorus that is discharged from the process with the wastewater might originate from the raw materials, e.g. aqueous hydrogen peroxide solution, and/or from auxiliary materials used in the process.
  • CN 107 986 987 an alcohol, e.g., cyclohexanol, based ammoximation process has been disclosed, which is a variant of the above- mentioned aldehyde or ketone based ammoximation process. Without being bound by theory it is assumed that in this process the alcohol is first converted into an aldehyde or a ketone, which is subsequently converted into an oxime. The addition of a pre-oxidation step makes this alcohol based ammoximation process, merely an extended version of the aldehyde or ketone based ammoximation process.
  • the process will produce a wastewater stream that contains at least the same amount of phosphorus, because the hydrogen peroxide consumption of this alcohol ammoximation variant will be even higher than in the traditional aldehyde or ketone based ammoximation process.
  • the oxime is prepared by reaction of a buffered hydroxylammonium phosphate solution and an aldehyde or ketone in the presence of a solvent.
  • the hydroxylammonium phosphate solution is obtained by selective hydrogenation of nitrate ions or nitrogen oxides in an aqueous phosphoric acid containing solution.
  • This process for the production of oximes is generally known as the HPO ® process and is licensed by Fibrant ® .
  • the HPO ® process is mainly applied for the production of cyclohexanone oxime.
  • the HPO ® cyclohexanone oxime process makes use of two recycling liquids - an inorganic liquid and an organic liquid - in which several reactions and operations take place (see e.g., H.J. Damme, J.T. van Goolen and A.H. de Rooij, Cyclohexanone oxime made without by-product (NH 4 ) 2 S0 4 , July 10, 1972, Chemical Engineering; pp 54/55 or Ullmann's Encyclopedia of industrial Chemistry, online publication of article on "Caprolactam", pp 8-10, Version of Record online: 25 May 2018, DOI: 10.1002/14356007.a05_031 , Copyright ⁇ 2018 Wiley-VCH Verlag GmbH & Co.
  • the inorganic liquid a phosphate-containing acidic aqueous solution, also containing ammonium, nitrate and/or nitrogen monoxide, is fed to a hydroxylamine formation zone, where hydroxylamine is produced. Hydroxylamine is formed via reduction of nitrate with hydrogen, which is catalysed by a heterogeneous catalyst, for example a palladium-containing catalyst with carbon as carrier.
  • the resulting mixture of the first reaction is a phosphate-containing acidic aqueous solution comprising a suspension of solid catalyst particles in a hydroxylamine solution.
  • the separated organic liquid that contains the formed cyclohexanone oxime is washed with water and the cyclohexanone oxime is recovered from the washed organic liquid by distillation.
  • All water that is chemically formed in the HPO ® process (see, e.g., Reaction 2) and Reaction 3)) and the water that is added to the process (e.g., water used to wash the separated organic liquid that contains the formed cyclohexanone oxime) is discharged from the process after steam stripping.
  • a typical HPO ® cyclohexanone oxime process discharges about 1.5 tons of wastewater per ton of produced cyclohexanone oxime. This wastewater contains only traces of organic components and low amounts of inorganic components including some phosphate. Typically, this wastewater is discharged to a biochemical wastewater treatment plant.
  • Phosphorus is a required nutrient for plants to live and is the limiting factor for plant growth in many aqueous ecosystems.
  • An oversupply of phosphorus e.g., due to discharge of wastewater that contains phosphate originating from cyclohexanone oxime producing processes, leads to overgrowth of plants and algae.
  • the terms eutrophication or hypertrophication are generally used to describe this process.
  • OECD Cooperation and Development
  • Another method applied to lower the phosphorus content in wastewater before being discharged is based on the addition of sufficient calcium, e.g., in the form of lime, to react with the phosphorus in the wastewater to form precipitates of e.g., calcium hydroxyapatite, brushite or dicalcium phosphate dehydrate, which are salts with a low solubility in water.
  • sufficient calcium e.g., in the form of lime
  • aluminium containing materials like aluminium sulphate, alum (e.g., sodium alum, potassium alum and ammonium alum) or clay are added.
  • Another phosphorus reducing method is based on precipitation of iron phosphate.
  • Wastewater treatment processes that apply one of the above mentioned methods (or a combination thereof) are often faced with nuisance formation of phosphate minerals in pipes, heat exchangers, and tanks due to the high levels of phosphate produced during anaerobic digestion of the solids.
  • the above mentioned methods inevitably produce large amounts of sludge due to the use of large amounts of chemicals and require complex post-treatments.
  • the produced materials do not have any economic value at all: mostly significant costs are associated with disposal or other after-treatment methods. And last but not least, the required phosphate discharge standards are often not reached by these methods.
  • processes for the production of an oxime that have phosphorus in their wastewater such as processes that are either based on selective reaction of an aldehyde or a ketone, ammonia, and hydrogen peroxide in the presence of a catalyst, or those processes that are based on the reaction of a buffered hydroxylammonium phosphate solution and an aldehyde or ketone in the presence of a solvent, whereby the hydroxylammonium phosphate solution is obtained by selective hydrogenation of nitrate ions or nitrogen oxides in an aqueous phosphoric acid containing solution, require a novel dephosphorization process for their wastewater.
  • the present inventors have discovered a process that significantly improves the dephosphorization of wastewater originating from processes for the production of oximes that are either based on selective reaction of an aldehyde or a ketone, ammonia, and hydrogen peroxide in the presence of a catalyst, or on the reaction of a buffered hydroxylammonium phosphate solution and an aldehyde or ketone in the presence of a solvent, whereby the hydroxylammonium phosphate solution is obtained by selective hydrogenation of nitrate ions or nitrogen oxides in an aqueous phosphoric acid.
  • the present invention provides an improved process for the production of an oxime, the process comprising:
  • a salt in which the molar ratio of N: P: Mg is about 1 : 1 : 1 can be ammonium magnesium phosphate and/or various hydrates thereof.
  • Nonlimiting examples of hydrates of ammonium magnesium phosphate include ammonium magnesium phosphate monohydrate (also often referred to as dittmarite), ammonium magnesium phosphate tetrahydrate (also often referred to as schertelite), and ammonium magnesium phosphate hexahydrate (also often referred to as struvite).
  • N, Mg and P are the symbols of the chemical elements nitrogen, magnesium and phosphorus, respectively.
  • the formed salt in which the molar ratio of N: Mg: P is about 1 : 1 : 1 can be amorphous or crystalline.
  • the formed salt in which the molar ratio of N: Mg: P is about 1 : 1 : 1 can also contain other compounds that do not have a molar ratio of N: Mg: P is about 1 : 1 : 1.
  • the formed salt in which the molar ratio of N: Mg: P is about 1 : 1 : 1 can consist of large sized particles that settle, fines that do not settle and
  • a person skilled in the art is familiar with separating a salt from an aqueous phase.
  • pretreatment techniques like coagulation and settling.
  • the sludge produced from biochemical wastewater treatment plants is enriched with phosphorus. After separation of the sludge from the effluent the phosphorus in the effluent from a biochemical wastewater treatment plant is reduced. Although a phosphate content in the intake of a biochemical wastewater treatment plant ranging from 3 to 10 mg/I (ppm) is quite common, other biochemical wastewater treatment plants are operated outside this optimal concentration window.
  • the inventors realized that it is advantageous to use the second aqueous phase as phosphate source of a biochemical wastewater treatment plant instead of dosing phosphate from an external source.
  • This solution not only leads to the saving of valuable chemical compounds like e.g., phosphoric acid, but also to an enhanced rate of dephosphorization of the second aqueous phase.
  • the process further comprises:
  • the effluent from the biochemical wastewater treatment plant comprises the third aqueous phase and might further contain solid material like e.g., sludge. It is advantageous to separate this solid material to a large extent from the third aqueous phase, whereby a solid material containing phase and a(n almost) clear third aqueous phase are formed.
  • Magnesium ammonium phosphate hexahydrate can be formed by the reaction:
  • the salt in which the molar ratio of N: Mg: P is about 1 : 1 : 1 is magnesium ammonium phosphate hexahydrate.
  • the formation of magnesium ammonium phosphate hexahydrate is carried out in a pH value range from 6 to 14, more preferably from 7 to 11 and most preferably from 8 to 10.
  • a pH value range from 6 to 14, more preferably from 7 to 11 and most preferably from 8 to 10.
  • the concentrations of Mg 2+ and NH 4+ ions decrease, while the concentration of P0 4 3 increases due to the greater availability of orthophosphate at higher pH values.
  • the formation of the salt in which the molar ratio of N: Mg: P is about 1 : 1 : 1 can be achieved by adjusting the pH value of the first aqueous phase. Adjustment of the pH value can be achieved in various ways. Typically, the pH value of the first aqueous phase can be adjusted by addition of caustic (either as solution, solid or as a slurry), ammonia or by mixing with a waste stream that provides the desired pH adjustment.
  • the effluent stream of an incinerator that contains sodium carbonate, sodium bicarbonate, sodium hydroxide and mixtures thereof, is very suitable for pH control. Such an effluent stream can either be a solution, solid or a slurry.
  • the formation of the salt is achieved by adjusting the pH value of the first aqueous phase to between about 6 and 14. According to a preferred embodiment of the process of the present invention the formation of the salt is achieved by addition of an effluent stream of an incinerator to the first aqueous phase.
  • a base such as e.g., NaOH.
  • Both the temperature, ranging from about ambient to boiling temperature, and the residence time of at least 15 minutes are not very critical.
  • the hydrolysis of trioctyl phosphate to phosphate in wastewater is above 99% in case the pH value, the temperature and the residence time are at least 10.5, 40°C, and 10 hrs, respectively.
  • the formation a salt in which the molar ratio of N: Mg: P is about 1 : 1 : 1 requires the presence of a sufficient concentration of magnesium ions.
  • concentration of magnesium ions in the first aqueous phase is insufficient, the concentration of magnesium ions can be increased in various ways.
  • the concentration of magnesium ions in the first aqueous phase is increased by the addition of magnesium ions from an external source such as a magnesium containing salt.
  • any magnesium containing salt can meet this requirement.
  • Especially suitable for this purpose are magnesium hydroxide, magnesium chloride and magnesium carbonate containing salts. These salts can be added either as a solution, as a solid or as a slurry.
  • the molar ratio of magnesium ions to phosphate ions is at least 1 : 1 , more preferably 1.1 : 1 , most preferably 1.25: 1. Higher ratios are even more preferred. However, much higher ratios are not desired because of the relative high costs of magnesium salts.
  • the formation of the salt is achieved by addition of a magnesium containing salt to the first aqueous phase.
  • the formation of a salt in which the molar ratio of N: Mg: P is about 1 : 1 : 1 requires the presence of a sufficient concentration of ammonium ions.
  • ammonium ions are present in wastewaters of processes for the production of an oxime.
  • the addition of ammonium from any source can overcome this shortage.
  • gaseous ammonia or aqueous ammonia solutions such as e.g. 25 wt.% NH 3 in water.
  • the molar ratio of ammonium ions to phosphate ions is at least 1 : 1 , more preferably at least 1.5: 1 and most preferably 2: 1. Higher ratios of a molar ratio of ammonium ions to phosphate ions above 2: 1 are even more preferred. However, much higher ratios are not desired because of restrictions regarding the content of ammonia in wastewater effluent.
  • the formation of the salt is achieved by addition of ammonium ions to the first aqueous phase.
  • the formation of the salt in step e. 1) is achieved by realizing a molar ratio of magnesium ions to phosphate ions of at least 1.15: 1 ; and a molar ratio of ammonium ions to phosphate ions of at least 1.5: 1 in the first aqueous phase.
  • ammonium salts e.g., ammonium chloride or ammonium sulphate
  • An aqueous waste stream or a purge of an ammonium sulphate crystallization plant is extremely suitable for enhancement of the ammonium ion concentration of the first aqueous phase.
  • Such a waste stream or a purge can also comprise other organic and inorganic impurities that e.g. originate from a caprolactam production process.
  • the inorganic impurities include sodium ions that originate from the caprolactam purification process.
  • the organic impurities include caprolactam and its derivatives.
  • the formation of the salt in step e. 1) is achieved by addition of a stream to the first aqueous phase that originates from an ammonium sulphate crystallization plant and comprises ammonium ions and at least one inorganic or organic impurity originating from a caprolactam production process.
  • the process of the present invention advantageously achieves a reduction of the phosphorous content by at least a factor of 10, preferably by a factor of 50, more preferably by a factor of 100, most preferred by a factor of 200 in the third aqueous phase compared to the first aqueous phase.
  • the final effluent of the process of the present invention contains less than 1.5 ppm, in particular less than 1 ppm, especially less than 0.5 ppm of phosphorous.
  • Oximes can be obtained by the reaction of aldehydes or ketones and hydroxylamine.
  • an aldehyde or a ketone is converted to an oxime with hydroxylamine.
  • the process for the production of an oxime is either an ammoximation process, in which in step a. an aldehyde or a ketone, ammonia, and hydrogen peroxide react in the presence of a catalyst or a process, in which first hydroxylamine is formed by selective reduction of nitrate followed by reaction of the formed hydroxylamine with the ketone cyclohexanone to form an oxime in step a.
  • the ketone is selected from butanone, cyclohexanone or cyclododecanone.
  • the oximes that are obtained by the conversion of butanone, cyclohexanone and cyclododecanone with hydroxylamine are butanone oxime, cyclohexanone oxime and cyclododecanone oxime, respectively.
  • the formed oxime is selected from butanone oxime, cyclohexanone oxime or
  • cyclododecanone oxime cyclododecanone oxime.
  • the ketone is cyclohexanone and the formed oxime is cyclohexanone oxime.
  • the obtained cyclohexanone oxime can be further reacted by Beckmann rearrangement to form caprolactam.
  • the Beckmann rearrangement can be performed both in the liquid and in the gas phase.
  • the formed caprolactam can be used as raw material for the production of polyamide-6.
  • the ketone is cyclodecanone and the formed oxime is cyclodecanone oxime. Thereafter, the obtained cyclododecanone oxime can be further reacted by Beckmann rearrangement to form laurolactam.
  • the formed laurolactam can be used as raw material for the production of polyamide-12.
  • a chemical plant is all apparatus necessary to manufacture or otherwise process the desired chemicals. This includes units for one or multiple chemical or physical operations, for example, heating up, cooling down, mixing, distillation, extraction and reaction. It further typically includes all auxiliary equipment, for example reflux units, coolant supply, pumps, heat exchangers and pipework.
  • auxiliary equipment for example reflux units, coolant supply, pumps, heat exchangers and pipework.
  • the exact structure of the chemical plant depends amongst others on the type and purity of the starting material(s) and the desired end product(s), but also on the scale and type of the process carried out. In case the processes carried out produce
  • the chemical plant also includes all apparatus parts necessary to convert the wastewater into an effluent that can be discharged into e.g., a sea, a river or a canal.
  • a continuous process is a process operating 24 hours per day, seven days per week with the exception of infrequent interruptions due to e.g., a process disturbance, a maintenance activity or for economic reasons.
  • a continuous process for the production of an oxime as used herein is a process in which an aldehyde or a ketone are fed without interrupting the process and whereby an oxime is withdrawn without interrupting the process.
  • the continuous process for the production of an oxime can be carried out at a constant rate or its rate can fluctuate over time.
  • the chemical plant for carrying out the process of the invention is preferably of industrial scale.
  • industrial scale means an oxime production rate of at least 1 ,000 kg of oxime per hour, more preferably at least 2,000 kg of oxime per hour, even more preferably at least 4,000 kg of oxime per hour, most preferably at least 6,000 kg of oxime per hour.
  • Converting an aldehyde or a ketone by a chemical reaction as used herein means that an aldehyde or a ketone is partly or completely transformed whereby an oxime is formed as product.
  • at least 50 mole % of the aldehyde or the ketone is converted into an oxime, more preferably at least 80 mole %, even more preferably at least 96 mole %, and most preferably at least 99 mole %.
  • oxime purification and recovery section wherein the formed oxime is purified and recovered
  • phosphate hexahydrate is formed and separated from an aqueous phase.
  • the chemical reaction section wherein the oxime is formed can comprise:
  • a phosphorus containing compound like e.g., aqueous hydrogen peroxide containing phosphorus compounds, or phosphoric acid.
  • a solvent like e.g., toluene or t-butanol
  • the oxime purification and recovery section wherein the formed oxime is purified and recovered can comprise:
  • an oxime comprising phase is washed with water and/or an aqueous solution (e.g., aqueous caustic); and
  • oxime is separated from other components (e.g., solvent like toluene, unconverted aldehyde or ketone).
  • phosphate is formed can comprise:
  • a unit in which an aqueous phase containing phosphorus compounds is separated from process liquid originating from the chemical reaction section like e.g., a liquid-liquid separator or a stripper;
  • an aqueous solution e.g., aqueous caustic
  • a stripping unit in which volatile organic compounds are (e.g., steam) stripped from an aqueous phase;
  • the dephosphorization section wherein solid magnesium ammonium phosphate hexahydrate is formed and separated from an aqueous phase can comprise:
  • magnesium ions and/or a source of ammonium ions are examples of magnesium ions and/or a source of ammonium ions.
  • a magnesium ammonium phosphate hexahydrate separation unit e.g., a filter
  • the biochemical wastewater treatment section can comprise:
  • filtration section in which colloidal suspensions of fine solids can be removed from wastewater by filtration
  • an oxidation section in which the biochemical oxygen demand of wastewater is reduced by biochemical oxidation and optionally also by chemical oxidation;
  • a polishing section to filter wastewater, which is discharged from the biochemical wastewater treatment section.
  • the polishing section to filter wastewater, which is discharged from the biochemical wastewater treatment section can comprise a filtration through a sand bed, in which mainly solid contaminants are removed.
  • the filtration section comprises a sand bed.
  • the ketone is cyclohexanone or cyclododecanone and the resulting cyclohexanone oxime or cyclododecanone oxime is further reacted by Beckmann rearrangement to form caprolactam or fauroiactam, respectively.
  • the oxime is cyclohexanone oxime.
  • Magnesium ammonium phosphate hexahydrate is a unique fertilizer because it provides three essential nutrients to plants: magnesium, nitrogen, and phosphorus. Besides its unique composition magnesium ammonium phosphate hexahydrate has slow release properties. Slow release properties as used herein mean that the magnesium ammonium phosphate releases its nutrients not (almost) instantaneously but over a course of time.
  • a fertilizer product comprising magnesium ammonium phosphate hexahydrate, obtainable by the process of the invention for the production of an oxime.
  • the process of the invention for the production of an oxime is much more ecologically beneficial than processes known in the art.
  • the product of such a process is also much more ecologically beneficial than products that are produced via other processes.
  • the special character of such a much more ecologically beneficial product can be guaranteed by e.g., certification.
  • a fertilizer product comprising magnesium ammonium phosphate hexahydrate, obtainable by the process of the invention for the production of an oxime.
  • cyclohexanone oxime obtainable by the process of the invention is the product resulting from the conversion of cyclohexanone.
  • the obtained cyclohexanone oxime has a content of the chemical compound cyclohexanone oxime that is at least 92 wt.%; more preferably at least 97 wt.%; even more preferably, it is at least 99 wt.%; still preferably at least 99.5 wt.%; most preferably at least 99.9 wt.%.
  • impurities cyclohexanone, toluene and water can be present.
  • FIG. 1 schematically shows a conventional state of the art plant for the production of cyclohexanone oxime and wastewater treatment.
  • FIG. 2 shows a plant according to the present invention, for the production of cyclohexanone oxime and wastewater treatment.
  • FIG. 3 schematically shows a cyclohexanone oxime production section based on HPO ® technology, which is an example of a cyclohexanone oxime production section [A] that is depicted in both FIG. 1 and FIG. 4.
  • Fig. 4 schematically shows a cyclohexanone oxime production section based on cyclohexanone ammoximation technology, which is an example of a cyclohexanone oxime production section [A] that is depicted in both FIG. 1 and FIG. 4.
  • FIG. 1 schematically shows a conventional state of the art plant for the production of cyclohexanone oxime and wastewater treatment that comprises a cyclohexanone oxime production section [A], a wastewater treatment plant [C] and a filtration section [D]
  • Cyclohexanone oxime production section [A] comprises a reaction section wherein cyclohexanone oxime is formed, and a cyclohexanone oxime separation and purification section.
  • the purified cyclohexanone oxime is discharged from cyclohexanone oxime production section [A] through line [1]
  • Wastewater that contains phosphorus is discharged from cyclohexanone oxime production section [A] through line [2]
  • organic compounds are removed to a large extent from wastewater that is charged through line [2]
  • wastewater from other plants is charged to the same wastewater treatment plant [C] (not shown in the Figure).
  • the removal of organic compounds is done by biochemical oxidation.
  • the hereby formed sludge, that contains a part of the phosphorus that is charged to the wastewater treatment plant [C] is discharged through line [8]
  • the treated wastewater, that contains less organic compounds than the wastewater that is charged to the wastewater treatment plant [C] is discharged through line [9],
  • filtration section [D] particulate solids are removed from the waste water that is charged through line [9].
  • Filtration section [D] might contain one or more sand bed filters and/or membrane filtration units.
  • the solids removed in filtration section [D] are discharged through line [10]
  • the obtained treated wastewater from filtration section [D] is discharged into e.g., a sea, a river or a canal through line [11].
  • FIG. 2 shows a plant according to the present invention, for the production of cyclohexanone oxime and wastewater treatment that comprises a cyclohexanone oxime production section [A], a dephosphorization section [B], wastewater treatment plant [C] and a filtration section [D]
  • Cyclohexanone oxime production section [A] comprises a reaction section wherein cyclohexanone oxime is formed, and a cyclohexanone oxime separation and purification section.
  • the purified cyclohexanone oxime is discharged from cyclohexanone oxime production section [A] through line [1] Wastewater that contains phosphorus is discharged from cyclohexanone oxime production section [A] through line [2]
  • magnesium ammonium phosphate hexahydrate is formed and separated from the wastewater that is charged through line [2].
  • wastewater from other plants is charged to the same
  • dephosphorization section [B] (not shown in the Figure).
  • pH adjustment chemicals are charged through line [3]
  • a source of magnesium ions is charged through line [4]
  • a source of ammonium ions is charged through line [5]
  • the formed magnesium ammonium phosphate hexahydrate is discharged through line [6]
  • the formed magnesium ammonium phosphate hexahydrate is further treated, e.g., dried or blended with other compounds, before being applied as fertilizer (not shown in the Figure).
  • the dephosphorized wastewater is discharged from dephosphorization section [B] through line [7]
  • the wastewater from cyclohexanone oxime production section [A] is first treated to convert organic phosphorus into phosphate before being charged to
  • organic compounds are removed to a large extent from wastewater that is charged through line [7]
  • wastewater from other plants is charged to the same wastewater treatment plant [C] (not shown in Figure).
  • the removal of organic compounds is done by biochemical oxidation.
  • the hereby formed sludge, that contains a part of the phosphorus that is charged to the wastewater treatment plant [B], is discharged through line [8]
  • the treated wastewater, that contains less organic compounds than the wastewater that is charged to the wastewater treatment plant [C] is discharged through line [9]
  • FIG. 3 schematically shows a cyclohexanone oxime production section based on HPO ® technology, which is an example of a cyclohexanone oxime production section [A] that is depicted in both FIG. 1 and FIG. 2.
  • Gaseous ammonia charged through line [a] is combusted with air charged through line [b] to an ammonia combustion unit, whereby NO x gases are formed. These NO x gases are absorbed in an aqueous phosphate containing solution, whereby nitrate is formed.
  • This nitrate loaded aqueous phosphate containing solution is charged to a hydroxylamine formation section, in which nitrate is catalytically reduced with hydrogen gas charged through line [c] to form
  • aqueous phosphate and hydroxylamine containing solution is contacted with an organic solution that contains fresh added cyclohexanone charged through line [d] and recycled cyclohexanone and solvent toluene, in the cyclohexanone oxime formation zone, whereby cyclohexanone oxime is formed.
  • An aqueous phosphate containing solution with low hydroxylamine content is discharged from the cyclohexanone oxime formation zone and is recycled via an NO x absorption unit to the hydroxylamine formation section.
  • a solution of cyclohexanone oxime in toluene that contains small amounts of phosphate is removed from the cyclohexanone oxime formation zone and is washed in the cyclohexanone oxime washing section with washing water charged through line [ej, whereby a washed solution of cyclohexanone oxime in toluene and water phase that contains phosphate is obtained.
  • the water phase that contains phosphate is separated from the solution of cyclohexanone oxime in toluene and is partly discharged as first water phase that contains phosphate and partly recycled into the process,
  • the washed solution of cyclohexanone oxime in toluene is distilled, whereby toluene and cyclohexanone are obtained that are recycled and cyclohexanone oxime that is discharged through line [1]
  • Reaction 2 hydroxylamine in the hydroxylamine formation section
  • Reaction 3 due to the formation of cyclohexanone oxime in the cyclohexanone oxime formation zone
  • This formed water has the tendency to accumulate in the aqueous phosphate solution.
  • Steam stripping of the aqueous phosphate solution is applied in order to balance the amount of water in the process, whereby a second water phase that contains phosphate is obtained.
  • Both the first water phase that contains phosphate and the second water phase that contains phosphate are treated in a stripping unit in which volatile organic compounds are removed.
  • the hereby obtained stripped aqueous phase is the phosphorus containing wastewater that is discharged from the cyclohexanone oxime production section [A] through line [2],
  • FIG. 4 schematically shows a cyclohexanone oxime production section based on cyclohexanone ammoximation technology, which is an example of a cyclohexanone oxime production section [A] that is depicted in both FIG. 1 and FIG. 2.
  • This aqueous cyclohexanone oxime and phosphorus compounds containing phase is extracted with toluene whereby an organic cyclohexanone oxime containing toluene phase and a first phosphorus compounds and organics containing wastewater stream are obtained.
  • the organic cyclohexanone oxime containing toluene phase is washed with (optionally caustic) washing water that is charged through line [i], whereby a washed solution of cyclohexanone oxime in toluene and a second phosphorus compounds and organics containing wastewater stream are obtained.
  • the second phosphorus compounds and organics containing wastewater stream is separated from the solution of cyclohexanone oxime in toluene and is discharged.
  • a distillation unit the washed solution of cyclohexanone oxime in toluene is distilled, whereby toluene and cyclohexanone are obtained that are (optionally) recycled and cyclohexanone oxime that is discharged through line [1]
  • Both the first phosphorus compounds and organics containing wastewater stream and the second phosphorus compounds and organics containing wastewater stream are combined and are discharged from cyclohexanone oxime production section [A] through line [2].
  • cyclohexanol is first converted into cyclohexanone through the action of hydrogen peroxide and then the cyclohexanone is converted into cyclohexanone oxime.
  • the present invention is illustrated by, but not intended to be limited to, the following examples.
  • a continuous HPO ® process for the production of cyclohexanone oxime in which first hydroxylamine is formed by selective reduction of nitrate followed by reaction of the formed hydroxylamine with cyclohexanone to form cyclohexanone oxime at about 70 °C, where after the formed cyclohexanone oxime is separated from the reaction mixture and whereby the generated wastewater is treated in a biochemical wastewater treatment plant was performed in a chemical plant, comprising:
  • This commercial chemical plant had on average an hourly output of about 25 t/h of cyclohexanone oxime, which is equivalent to an annual plant output of approximately 200 kta of cyclohexanone oxime (assuming 8000 effective production hours per year).
  • the main raw materials that were charged to the cyclohexanone oxime production section of this chemical plant were ammonia, air, hydrogen gas, and cyclohexanone.
  • small amounts of phosphoric acid and toluene were charged to compensate for losses and washing water was charged to the
  • cyclohexanone oxime washing section The wastewater that is discharged from the cyclohexanone oxime production section is mixed with wastewaters from other chemical plants on the caprolactam production site.
  • These other chemical plants include a chemical plant for cyclohexanone production by oxidation of cyclohexane, a chemical plant for caprolactam production by liquid phase Beckmann rearrangement of cyclohexanone oxime followed by neutralization with ammonia, a chemical plant for caprolactam purification and a chemical plant for ammonium sulphate crystallization.
  • the total amount of wastewaters that are charged to the biochemical wastewater treatment plant is about 150 m 3 /h and contains on average about 120 ppm phosphorus (in the form of phosphate).
  • the treated wastewater that is discharged from the filtration section for removal of solids that is located downstream of the biochemical wastewater treatment plant contains on average about 110 ppm phosphorus (in the form of phosphate).
  • Example 1 the cyclohexanone oxime production section, the biochemical wastewater treatment plant with sludge removal, and the filtration section located downstream of the biochemical wastewater treatment plant for removal of solids were the same as the cyclohexanone oxime production section, the biochemical wastewater treatment plant with sludge removal, and the filtration section located downstream of the biochemical wastewater treatment plant for removal of solids in Comparative Experiment A.
  • the chemical plant in Example 1 is provided with a dephosphorization section.
  • a continuous HPO ® process for the production of cyclohexanone oxime in which first hydroxylamine is formed by selective reduction of nitrate followed by reaction of the formed hydroxylamine with cyclohexanone to form cyclohexanone oxime at about 70 °C, where after the formed cyclohexanone oxime is separated from the reaction mixture and whereby the generated wastewater is treated in a dephosphorization section and consequently in a biochemical wastewater treatment plant was performed in a chemical plant, comprising:
  • This commercial chemical plant had on average an hourly output of about 25 t/h of cyclohexanone oxime, which is equivalent to an annual plant output of approximately 200 kta of cyclohexanone oxime (assuming 8000 effective production hours per year).
  • the main raw materials that were charged to the cyclohexanone oxime production section of this chemical plant were ammonia, air, hydrogen gas, and cyclohexanone.
  • small amounts of phosphoric acid and toluene were charged to compensate for losses and washing water was charged to the
  • the wastewater that is discharged from the cyclohexanone oxime production section is mixed with wastewaters from other chemical plants on the caprolactam production site.
  • These other chemical plants include a chemical plant for cyclohexanone production by oxidation of cyclohexane, a chemical plant for caprolactam production by liquid phase Beckmann rearrangement of cyclohexanone oxime followed by neutralization with ammonia, a chemical plant for caprolactam purification and a chemical plant for ammonium sulphate crystallization.
  • the total amount of wastewaters that are charged to the dephosphorization section is about 150 m 3 /h and contains on average about
  • the pH value is maintained at about 9 by addition of caustic.
  • the molar ratio of P: Mg: N is maintained at about 1 : 1.2: 2 by addition of MgCI 2 and ammonium sulphate containing purge liquid from the ammonium sulphate crystallization plant.
  • the hereby formed magnesium ammonium phosphate hexahydrate is separated from the wastewater and is discharged. The discharged magnesium ammonium phosphate hexahydrate is after drying applied as fertilizer.
  • the wastewater that is discharged from the dephosphorization section contains about 5 ppm phosphorus (in the form of phosphate) is charged to the biochemical wastewater treatment plant with sludge removal.
  • the treated wastewater that is discharged from the filtration section for removal of solids that is located downstream of the biochemical wastewater treatment plant contains less than 0.5 ppm phosphorus (in the form of phosphate).
  • hexahydrate is obtained that can be used as fertilizer.
  • a continuous process for the production of cyclohexanone oxime in which cyclohexanone, ammonia, and hydrogen peroxide react in the presence of a TS-1 catalyst and t-butanol as solvent at about 85 °C and whereby the formed cyclohexanone oxime is separated from the reaction mixture by extraction in toluene, washed with an aqueous caustic solution and then separated by distillation and whereby the generated wastewaters are treated in a biochemical wastewater treatment plant was performed in a chemical plant, comprising:
  • a washing section wherein the organic cyclohexanone oxime containing toluene phase is washed with caustic washing water, whereby a washed solution of cyclohexanone oxime in toluene and a second phosphorus compounds and organics containing wastewater stream are obtained; - a cyclohexanone oxime distillation section;
  • This chemical plant had on average an hourly output of about 12.5 t/h of cyclohexanone oxime, which is equivalent to an annual plant output of
  • cyclohexanone oxime approximately 100 kta of cyclohexanone oxime (assuming 8000 effective production hours per year).
  • the main raw materials that were charged to the cyclohexanone oxime production section of this chemical plant were ammonia, 27 wt.% aqueous hydrogen peroxide, and cyclohexanone.
  • the used 27 wt.% aqueous hydrogen peroxide is produced in a hydrogen peroxide plant that is based on the well-known anthraquinone technology.
  • the phosphorus content of 27 wt.% aqueous hydrogen peroxide is about 0.5 kg trioctyl phosphate per ton of 27 wt.% aqueous H 2 0 2 and about 1 kg phosphoric acid per ton of 27 wt.% aqueous H 2 0 2 .
  • small amounts of t-butanol and toluene were charged to the cyclohexanone oxime production section of this chemical plant to compensate for losses and caustic washing water was charged to the cyclohexanone oxime washing section.
  • All wastewaters, including the first phosphorus compounds and organics containing wastewater stream and the second phosphorus compounds and organics containing wastewater stream that are discharged from cyclohexanone oxime production section are combined and are charged to the biochemical wastewater treatment plant with sludge removal.
  • the treated wastewater that is discharged from the filtration section for removal of solids that is located downstream of the biochemical wastewater treatment plant contains on average about 150 ppm phosphorus (partly in the form of phosphate and partly in the form of organic phosphorus).
  • Example 2 the cyclohexanone oxime production section, the biochemical wastewater treatment plant with sludge removal, and the filtration section located downstream of the biochemical wastewater treatment plant for removal of solids were the same as the cyclohexanone oxime production section, the biochemical wastewater treatment plant with sludge removal, and the filtration section located downstream of the biochemical wastewater treatment plant for removal of solids in Comparative Experiment B.
  • the chemical plant in Example 2 is provided with a dephosphorization section.
  • a continuous process for the production of cyclohexanone oxime in which cyclohexanone, ammonia, and hydrogen peroxide react in the presence of a TS-1 catalyst and t-butanol as solvent at about 85 °C and whereby the formed cyclohexanone oxime is separated from the reaction mixture by extraction in toluene, washed with an aqueous caustic solution and then separated by distillation and whereby the generated wastewaters are treated in a biochemical wastewater treatment plant was performed in a chemical plant, comprising:
  • toluene phase is washed with caustic washing water, whereby a washed solution of cyclohexanone oxime in toluene and a second phosphorus compounds and organics containing wastewater stream are obtained;
  • This chemical plant had on average an hourly output of about 12.5 t/h of cyclohexanone oxime, which is equivalent to an annual plant output of
  • cyclohexanone oxime approximately 100 kta of cyclohexanone oxime (assuming 8000 effective production hours per year).
  • the main raw materials that were charged to the cyclohexanone oxime production section of this chemical plant were ammonia, 27 wt.% aqueous hydrogen peroxide, and cyclohexanone.
  • the used 27 wt.% aqueous hydrogen peroxide is produced in a hydrogen peroxide plant that is based on the well-known anthraquinone technology.
  • the phosphorus content of 27 wt.% aqueous hydrogen peroxide is about 0.5 kg trioctyl phosphate per ton of 27 wt.% aqueous H 2 0 2 and about 1 kg phosphoric acid per ton of 27 wt.% aqueous H 2 0 2 .
  • small amounts of t-butanol and toluene were charged to the cyclohexanone oxime production section of this chemical plant to compensate for losses and caustic washing water was charged to the cyclohexanone oxime washing section.
  • organic phosphorus conversion unit All wastewaters, including the first phosphorus compounds and organics containing wastewater stream and the second phosphorus compounds and organics containing wastewater stream that are discharged from cyclohexanone oxime production section are combined and are charged to the organic phosphorus conversion unit.
  • organic phosphorus conversion organic phosphorus compounds like e.g., trioctyl phosphate, are almost completely hydrolyzed under alkaline conditions.
  • the pH value, temperature and residence time in this unit are maintained at about 11 , 50°C, and 8 hrs, respectively.
  • the pH value is adjusted by dosing of NaOH.
  • the treated wastewater that is discharged from the organic phosphorus conversion unit is charged to the dephosphorization section.
  • the pH value is maintained at about 9.
  • the molar ratio of P: Mg: N is maintained at about 1 :
  • magnesium ammonium phosphate hexahydrate is separated from the wastewater and is discharged.
  • the discharged magnesium ammonium phosphate hexahydrate is after drying applied as fertilizer.
  • the wastewater that is discharged from the dephosphorization section is charged to the biochemical wastewater treatment plant with sludge removal.
  • the treated wastewater that is discharged from the filtration section for removal of solids that is located downstream of the biochemical wastewater treatment plant contains less than 0.5 ppm phosphorus (in the form of phosphate).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Removal Of Specific Substances (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un procédé de production d'une oxime, le processus comprenant : a. convertir un aldéhyde ou une cétone par une réaction chimique en une oxime à une température de 15 à 115 °C, ce par quoi un mélange réactionnel comprenant l'oxime formée est obtenu; b. récupérer l'oxime formée à partir du mélange réactionnel; c. produire une première phase aqueuse qui contient des ions phosphate; d. réduire la teneur en ions phosphate dans la première phase aqueuse, moyennant quoi une seconde phase aqueuse est formée; et e. décharger la seconde phase aqueuse, la réduction de la teneur en ions phosphate dans la première phase aqueuse étant obtenue par 1 ) la formation d'un sel dans lequel le rapport molaire de N: Mg: P est d'environ 1: 1: 1; et 2) séparer le sel dans lequel le rapport molaire de N: Mg: P est d'environ 1: 1: 1 à partir de la seconde phase aqueuse; un produit d'engrais comprenant un hexahydrate de phosphate d'ammonium de magnésium obtenu à partir de celui-ci; de la cyclohexanone-oxime obtenue à partir de celui-ci; et une plante chimique appropriée pour la production d'une oxime.
PCT/EP2019/077744 2018-10-17 2019-10-14 Processus et installation améliorés pour la production d'oximes Ceased WO2020078884A1 (fr)

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