DK155932B - METHOD OF PREPARING ACRYLIC ACID OR METHACRYLIC ACID - Google Patents

METHOD OF PREPARING ACRYLIC ACID OR METHACRYLIC ACID Download PDF

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DK155932B
DK155932B DK436074AA DK436074A DK155932B DK 155932 B DK155932 B DK 155932B DK 436074A A DK436074A A DK 436074AA DK 436074 A DK436074 A DK 436074A DK 155932 B DK155932 B DK 155932B
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catalyst
range
reaction
methacrolein
acid
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DK436074AA
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DK155932C (en
DK436074A (en
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Masaaki Kato
Hiroshi Sonobe
Hiromichi Ishii
Masao Kobayashi
Kantaro Yamada
Teruhiko Yoshioka
Hideo Matsuzawa
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Mitsubishi Rayon Co
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872Alkali or alkaline earth metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/30Tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876Arsenic, antimony or bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877Vanadium, tantalum, niobium or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

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

Description

DK 155932 BDK 155932 B

Opfindelsen angår en fremgangsmåde til fremstilling af acrylsyre eller methacrylsyre ved .katalytisk: oxidation af acrolein eller methacrolein i gasfasen ved en temperatur på 240-390 °C med molekylært oxygen.The invention relates to a process for preparing acrylic acid or methacrylic acid by catalytic: oxidation of acrolein or methacrolein in the gas phase at a temperature of 240-390 ° C with molecular oxygen.

Der kendes forskellige katalysatorer til anvendelse ved katalytisk gasfase-oxidation af umættede aldehyder. F.eks. kan nævnes katalysatorer, som er angivet i US patentskrifterne nr. 3 475 488, 3 567 773, 3 646 127, 3 649 684 og 3 686 294 og DE patentskrift nr. 2 251 364. Blandt disse katalysatorer udviser en katalysator af molybden-vanadium-typen en udmærket virkning ved oxidation af acrolein, men denne katalysator er ikke så egnet til oxidation af methacrolein. En katalysator af phosphor-molybden-arsen-type giver gode resultater ved oxidation af methacrolein, når den har en specifik sammensætning, men den er stadig utilstrækkelig og indebærer problemer, som skal løses. F.eks. har den en meget kort katalysatorlevetid. Katalysatorer af anden type giver ikke gode resultater ved oxidation af methacrolein.Various catalysts are known for use in catalytic gas phase oxidation of unsaturated aldehydes. Eg. catalysts disclosed in U.S. Patent Nos. 3,475,488, 3,567,773, 3,646,127, 3,649,684 and 3,686,294 and DE Patent Nos. 2,251,364. Among these catalysts, a catalyst of molybdenum vanadium type has an excellent effect on the oxidation of acrolein, but this catalyst is not so suitable for the oxidation of methacrolein. A phosphorus-molybdenum-arsenic-type catalyst gives good results in methacrolein oxidation when it has a specific composition, but it is still insufficient and presents problems that need to be addressed. Eg. it has a very short catalyst life. Second type catalysts do not produce good results in the oxidation of methacrolein.

Ved forsøg med henblik på at forbedre sådanne ulemper ved denne katalysator af phosphor-molybden-arsen-type har det vist sig, at når en ammoniumgruppe inkorporeres i en katalysator af denne type, og der samtidig er mindst et specifikt metal til stede i katalysatorsystemet, kan katalysatorens levetid forlænges stærkt, medens aktiviteten og selektiviteten opretholdes på et højt niveau. Opfindelsen bygger på denne erkendelse.In attempts to ameliorate such disadvantages of this phosphorus-molybdenum-arsenic type catalyst, it has been found that when an ammonium group is incorporated into a catalyst of this type and at least one specific metal is present in the catalyst system, For example, the catalyst life can be greatly extended while maintaining activity and selectivity at a high level. The invention is based on this realization.

Opfindelsens formål er således at angive en fremgangsmåde til fremstilling af acrylsyre eller methacrylsyre i højt udbytte ud fra acrolein eller methacrolein ved anvendelse af en katalysator, som har en lang levetid, og som giver umættede carboxylsyrer i højt udbytte, når den anvendes til katalytisk oxidation af umættede aldehyder.Thus, the object of the invention is to provide a process for producing high yield acrylic acid or methacrylic acid from acrolein or methacrolein using a long-life catalyst which provides high yield unsaturated carboxylic acids when used for catalytic oxidation of unsaturated aldehydes.

Fremgangsmåden ifølge opfindelsen er ejendommelig ved det i krav l's kendetegnende del anførte.The process according to the invention is characterized by the characterizing part of claim 1.

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Atomforholdet for hver komponent i den omhandlede katalysator er kritisk, og hvis atomforholdet er uden for det angivne område, kan der ikke opnås en katalysator med tilstrækkelige egenskaber. Mængden af det metalelement, som repræsenteres ved X i den i krav 1 angivne formel, kan vælges inden for et område, udtrykt. ved atomforholdet i forhold til molybden, på 0,003-1· Når vanadium, wolfram, kobber, jern eller mangan anvendes som metallet X, foretrækkes det at atomforholdet af metallet X i forhold til molybden er inden for et område på 0,003-0,25, især 0,006-0,2. Når to eller flere sådanne metaller er til stede, foretrækkes det, at summen af atomforholdene af metallerne i forhold til molybden er inden for det ovenstående område. Hvis atomforholdet er under det ovenstående område, kan der ikke opnås en tilstrækkelig virkning, og hvis atomforholdet er over det ovenstående område, forlænges katalysatorens levetid yderligere, men selektiviteten formindskes. Når tin anvendes som metallet X, foretrækkes det at atomforholdet i forhold til molybden er inden for et område på 0,003-1, især 0,006-0,5. I tilfælde af at der anvendes en kombination af tin og et metal udvalgt blandt vanadium, wolfram, kobber, jern og mangan som metalkomponenten X, foretrækkes det, at summen af atomforholdene af tin og det andet metal er inden for et område på 0,003-1, især 0,01-0,5, og at atomforholdet af det andet metal i forhold til molybden er mindre end 0,25, især mindre end 0,2.The atomic ratio of each component of the catalyst in question is critical and if the atomic ratio is outside the specified range, a catalyst with sufficient properties cannot be obtained. The amount of the metal element represented by X in the formula set forth in claim 1 may be selected within a range expressed. at atomic to molybdenum ratio of 0.003-1 · When vanadium, tungsten, copper, iron or manganese is used as the metal X, it is preferred that the atomic ratio of the metal X to molybdenum be in the range of 0.003-0.25, especially 0.006-0.2. When two or more such metals are present, it is preferred that the sum of the atomic ratios of the metals relative to molybdenum is within the above range. If the atomic ratio is below the above range, a sufficient effect cannot be obtained and if the atomic ratio is above the above range, the catalyst life is further extended but the selectivity is diminished. When tin is used as the metal X, it is preferred that the atomic ratio to molybdenum is within a range of 0.003-1, especially 0.006-0.5. In the case of using a combination of tin and a metal selected from vanadium, tungsten, copper, iron and manganese as the metal component X, it is preferred that the sum of the atomic ratios of tin and the other metal be within a range of 0.003-1. , in particular 0.01-0.5, and that the atomic ratio of the second metal to molybdenum is less than 0.25, especially less than 0.2.

I tilfælde af at tin anvendes som metallet X, er reduktionen af selektiviteten ikke så betydelig, selv hvis det er til stede i en relativ stor mængde sammenlignet med et andet metal, og derfor kan der forventes en stærk forbedring af katalysatorens levetid. Blandt metalelementerne repræsenteret ved X er kobber det mest foretrukne.In the case of tin being used as the metal X, the reduction in selectivity is not so significant, even if present in a relatively large amount compared to another metal, and therefore a strong improvement in catalyst life can be expected. Of the metal elements represented by X, copper is the most preferred.

Mængden af et alkalimetal repræsenteret ved Y i den i krav 1 angivne formel vælges inden for et område, udtrykt ved atomforholdet i forhold til molybden, på 0-0,17, især 0,001-0,12. Hvis mængden af alkalimetallet Y ér udover det ovenstående område, iagttages en reduktion af selektiviteten.The amount of an alkali metal represented by Y in the formula of claim 1 is selected within a range, expressed by the atomic to molybdenum ratio, of 0-0.17, especially 0.001-0.12. If the amount of the alkali metal Y is in addition to the above range, a reduction in the selectivity is observed.

I den omhandlede katalysator antages det, at ammoniumgruppen er til stede i form af et salt. Ammoniumgruppen inkorporeres i kata- 3In the catalyst in question, it is believed that the ammonium group is present in the form of a salt. The ammonium group is incorporated into the cat 3

DK 155932 BDK 155932 B

lysatoren i en mængde på 0,01-0,3 molekyler pr. atom molybden, fortrinsvis 0,01-0,2 molekyler.the lysator in an amount of 0.01-0.3 molecules per atomic molybdenum, preferably 0.01-0.2 molecules.

Den kemiske tilstand af hvert komponentelement i katalysatoren er meget kompliceret, og det er ikke blevet fuldstændigt oplyst, i hvilken kemisk tilstand hvert element er til stede i katalysatoren. Imidlertid opfattes det, at hver komponent ikke er til stede i form af et blot og bart oxid, men at katalysatoren har form af en heteropolysyreforbindelse, og at ammoniumgruppen er til stede i form af et salt af denne heteropolysyre. Ifølge opfindelsen foretrækkes det ikke, at al heteropolysyren i katalysatoren er kombineret med ammoniumgruppen til dannelse af et salt, fordi den ønskede reaktion ikke skrider frem i dette tilfælde.The chemical state of each component element of the catalyst is very complicated and it has not been fully disclosed in what chemical state each element is present in the catalyst. However, it is believed that each component is not present in the form of a bare and bare oxide, but that the catalyst is in the form of a heteropoly acid compound and that the ammonium group is in the form of a salt of this heteropoly acid. According to the invention, it is not preferred that all the heteropoly acid in the catalyst is combined with the ammonium group to form a salt, because the desired reaction does not proceed in this case.

Hvis, i modsætning hertil, hver komponent er til stede i form af en heteropolysyre uden dannelse af et salt med ammoniumgruppen, dekomponeres heteropolysyrens anionstruktur hurtigt til oxider, medens oxidationen skrider frem ved en temperatur over 300°C, og aktiviteten falder. I så fald reduceres aktiviteten til afta-gelse af hydrogen fra det umættede aldehyd, og der kan ikke opnås en katalysator med høj aktivitet. Hvis imidlertid heteropolysyren med en protonafgivende aktivitet og et ammoniumsalt deraf er til stede sammen i katalysatoren, kan anionstrukturen opretholdes mere stabilt i heteropolysyren end i det tilfælde, hvor kun heteropolysyren er til stede i katalysatoren, med det resultat at selektiviteten forbedres og katalysatorens levetid samtidig kan forlænges.In contrast, if each component is present in the form of a heteropoly acid without the formation of a salt with the ammonium group, the anionic structure of the heteropoly acid is rapidly decomposed to oxides, while the oxidation proceeds at a temperature above 300 ° C and the activity decreases. In this case, the activity of removing hydrogen from the unsaturated aldehyde is reduced and a high activity catalyst cannot be obtained. However, if the heteropoly acid with a proton-releasing activity and an ammonium salt thereof is present together in the catalyst, the anion structure can be maintained more stable in the heteropoly acid than in the case where only the heteropoly acid is present in the catalyst, with the result that the selectivity is improved and the catalyst lifetime can simultaneously extended.

Når der inkorporeres et metalelement repræsenteret ved X i katalysatoren bestående af molybden, phosphor, arsen, en ammoniumgruppe og oxygen, kan katalysatorens levetid forbedres stærkt. Grunden hertil er ikke fuldstændig oplyst, men i betragtning af det kendte faktum, at aktiviteten og selektiviteten i en molybden-holdig katalysator reduceres, når koncentrationen af adsorberet oxygen formindskes, fortolkes det således, at koncentrationen af adsorberet oxygen forhøjes ved tilstedeværelsen af elementet X, og at aktiviteten derfor forhøjes, og katalysatorens levetid forlænges.When incorporating a metal element represented by X in the catalyst consisting of molybdenum, phosphorus, arsenic, an ammonium group and oxygen, the lifetime of the catalyst can be greatly improved. The reason for this is not fully elucidated, but given the known fact that the activity and selectivity of a molybdenum-containing catalyst are reduced as the concentration of adsorbed oxygen is reduced, it is interpreted as increasing the concentration of adsorbed oxygen by the presence of element X, and that the activity is therefore increased and the catalyst life is extended.

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DK 155932 BDK 155932 B

Den omhandlede katalysator varmebehandles ved en temperatur på 300-440°C, før den anvendes til reaktionen. En foretrukken varmebehandlingstemperatur er inden for området 360-430°C. Hvis varmebehandlingstemperaturen overskrider 440°C, formindskes både aktiviteten og selektiviteten af katalysatoren, og hvis varmebehandlingstemperaturen overskrider 460°C, bliver den nævnte reduktion meget tydelig. Således er der i den katalysator, som skal anvendes ved fremgangsmåden ifølge opfindelsen, en bestemt øvre grænse for varmebehandlingstemperaturen. På den anden side er den nedre grænse for varmebehandlingstemperaturen ikke så kritisk, men ved en varmebehandlingstemperatur på under 300°C er det vanskeligt at opnå en katalysator med stabile egenskaber. Varmebehandlingstiden varierer afhængigt af. varmebehandlingstemperaturen, men i almindelighed foretrækkes det, at varmebehandlingen udføres i fra 30 minutter til flere dage. Det er ønskeligt, at varmebehandlingen udføres i luft eller luft fortyndet med en inert gas. Om nødvendigt er det muligt som behandlingsatmosfære at anvende luft, hvori der er inkorporeret et reducerende stof i en lav koncentration.The present catalyst is heat treated at a temperature of 300-440 ° C before being used for the reaction. A preferred heat treatment temperature is in the range of 360-430 ° C. If the heat treatment temperature exceeds 440 ° C, both the activity and selectivity of the catalyst are diminished, and if the heat treatment temperature exceeds 460 ° C, the said reduction becomes very apparent. Thus, in the catalyst to be used in the process of the invention, there is a definite upper limit to the heat treatment temperature. On the other hand, the lower limit of the heat treatment temperature is not so critical, but at a heat treatment temperature below 300 ° C it is difficult to obtain a catalyst with stable properties. The heat treatment time varies depending on. heat treatment temperature, but generally it is preferred that the heat treatment be carried out for from 30 minutes to several days. It is desirable that the heat treatment be carried out in air or air diluted with an inert gas. If necessary, it is possible, as a treatment atmosphere, to use air in which a reducing agent is incorporated in a low concentration.

Fremstillingen af den omhandlede katalysator kan udføres ved kendte metoder inden for teknikken. Det er ønskeligt, at udgangsmaterialerne blandes intimt med hinanden, men blandingsmetoden er ikke særlig kritisk. Blot uregelmæssig fordeling af komponenterne undgås, kan enhver af de konventionelle metoder, såsom ind-dampning til tørhed, fældning, oxidblanding og lignende, anvendes til fremstilling af katalysatoren.The preparation of the present catalyst can be carried out by known methods in the art. It is desirable that the starting materials be intimately mixed, but the mixing method is not very critical. By simply irregular distribution of the components being avoided, any of the conventional methods such as evaporation to dryness, precipitation, oxide mixture and the like can be used to prepare the catalyst.

Som udgangsmaterialer for katalysatoren anvendes ammoniumforbin-delser, såsom ammoniummolybdat, ammoniumphosphat, ammoniumphos-phomolybdat, ammoniumarsenomolybdat osv. Elementer repræsenteret ved X anvendes i form af oxider, nitrater, ammoniumsalte og lignende, og alkalimetalelementerne repræsenteret ved Y anvendes i form af oxider, nitrater, hydroxider og lignende.As starting materials for the catalyst, ammonium compounds such as ammonium molybdate, ammonium phosphate, ammonium phosphomolybdate, ammonium arsenomolybdate, etc., elements represented by X are used in the form of oxides, nitrates, ammonium salts and the like, and the hydroxides and the like.

Når katalysatorkomponenterne anvendes i form af ammoniumsalte, såsom de ovennævnte, opnås indførelsen af ammoniumgruppen i katalysatoren igennem sådanne ammoniumsalte. I tilfælde af at der ikke anvendes sådanne ammoniumsalte som udgangsmateriale,anvendes for-When the catalyst components are used in the form of ammonium salts, such as those mentioned above, the introduction of the ammonium group into the catalyst is achieved through such ammonium salts. In case no such ammonium salts are used as starting material,

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trinsvis vandig ammoniak. F.eks. kan en homogen blanding til brug ved fremstilling af katalysatoren opnås ved at opløse en hidtil anvendt katalysator af phosphor-molybden-arsen-type i vandig ammoniak og sætte de andre metalkomponenter til den resulterende opløsning.stepwise aqueous ammonia. Eg. For example, a homogeneous mixture for use in the preparation of the catalyst can be obtained by dissolving a previously used phosphorus-molybdenum-arsenic type catalyst in aqueous ammonia and adding the other metal components to the resulting solution.

En homogen blanding af udgangsmaterialerne tørres og varmebehandles ved en temperatur på 300-440°C i fra 30 minutter til flere dage, hvorved der kan opnås en katalysator, hvori ammoniumgruppen er inkorporeret. Den inkorporerede mængde af ammoniumgruppen i katalysatoren er 0,01-0,3 molekyler pr. atom molybden.A homogeneous mixture of the starting materials is dried and heat-treated at a temperature of 300-440 ° C for from 30 minutes to several days, thereby obtaining a catalyst in which the ammonium group is incorporated. The incorporated amount of the ammonium group in the catalyst is 0.01-0.3 molecules per minute. atom molybdenum.

Som en anden metode til indførelse af ammoniumgruppen i katalysatoren kan der nævnes en metode, som består i behandling af en deaktiveret katalysator med ammoniak eller vandig ammoniak. Hvis f.eks. en katalysator, som er deaktiveret ved brug ved høj temperatur eller i lang tid, behandles i en reaktionsbeholder med flydende eller gasformig vandig ammoniak, kan der indføres en foreskreven mængde af ammoniumgruppen.As another method for introducing the ammonium group into the catalyst, there may be mentioned a method which consists in treating a deactivated catalyst with ammonia or aqueous ammonia. For example, If a catalyst which is deactivated by use at high temperature or for a long time is treated in a reaction vessel with liquid or gaseous aqueous ammonia, a prescribed amount of the ammonium group may be introduced.

Katalysatoren, som anvendes ved fremgangsmåden ifølge opfindelsen, kan indføres i reaktionen i båret form på en inert bærer, såsom aluminiumoxid, siliciumcarbid og perlit, eller i fortyndet form med et sådant inert stof. Hvis indholdet af en sådan bærer er for stort i den samlede katalysatorblanding, formindskes katalysatorens tilsyneladende aktivitet; derfor er det ønskeligt, at indholdet af bæreren i den samlede katalysatorblanding er mindre end 70 vægtpct.The catalyst used in the process of the invention can be introduced into the reaction in supported form on an inert carrier such as alumina, silicon carbide and perlite, or in dilute form with such an inert substance. If the content of such a carrier is too high in the total catalyst mixture, the apparent activity of the catalyst is diminished; therefore, it is desirable that the content of the carrier in the total catalyst mixture be less than 70% by weight.

Den type reaktionsbeholder, hvori ovennævnte katalysator pakkes, er ikke særlig kritisk, og der kan anvendes enten en reaktionsbeholder af typen med fast leje eller en reaktionsbeholder af typen med fluidiseret leje ved fremgangsmåden ifølge opfindelsen.The type of reaction vessel in which the above catalyst is packed is not very critical and either a fixed bed reaction vessel or a fluid bed reaction vessel can be used in the process of the invention.

Det umættede aldehyd, som skal oxideres ved fremgangsmåden ifølge opfindelsen, omfatter acrolein og methacrolein, og om ønsket kan der anvendes en blanding af acrolein og methacrolein som udgangsmateriale. Fremgangsmåden ifølge opfindelsen er særlig effektiv til oxidation af methacrolein. Methacrolein, som er opnået ved 6The unsaturated aldehyde to be oxidized by the process of the invention comprises acrolein and methacrolein, and if desired, a mixture of acrolein and methacrolein can be used as starting material. The process of the invention is particularly effective for the oxidation of methacrolein. Methacrolein obtained at 6

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katalytisk oxidation af isobutylen eller tertiært butanol, kan anvendes som det er, eller efter at det er renset.catalytic oxidation of isobutylene or tertiary butanol can be used as is or after it is purified.

Koncentrationen af det umættede aldehyd i tilførselsgassen kan varieres inden for et bredt område, men det foretrækkes i almindelighed, at koncentrationen af det umættede aldehyd er inden for et område på 1-20 volumenprocent, især 3-15 volumenprocent. Molekylært oxygen anvendes som oxidationsmidlet ved fremgangsmåden ifølge opfindelsen, og fra et økonomisk synspunkt foretrækkes det at anvende luft. Om nødvendigt kan der anvendes luft beriget med rent oxygen« Det foretrækkes, at koncentrationen af oxygen i tilførselsklassen, udtrykt ved molforholdet i forhold til det umættede aldehyd, er inden for et område på 0,3-4, især 0,4-2,5.The concentration of the unsaturated aldehyde in the feed gas can be varied within a wide range, but it is generally preferred that the concentration of the unsaturated aldehyde is in a range of 1-20% by volume, especially 3-15% by volume. Molecular oxygen is used as the oxidizing agent in the process of the invention, and from an economic point of view it is preferable to use air. If necessary, air enriched with pure oxygen may be used. "It is preferred that the concentration of oxygen in the feed class, expressed by the molar ratio to the unsaturated aldehyde, is within a range of 0.3-4, especially 0.4-2, 5th

Den gasformige udgangsblanding kan fortyndes med sådanne inerte gasser som nitrogen, damp, carbondioxid og lignende.The gaseous starting mixture can be diluted with such inert gases as nitrogen, steam, carbon dioxide and the like.

Oxidationsreaktionen udføres under et tryk på fra atmosfæretryk til flere atmosfærer. Rumhastigheden af tilførselsgassen varierer afhængigt af reaktionstemperåtureii og -trykket, men det foretrækkes i almindelighed, at den gasformige udgangsblanding tilføres med en rumhastighed på 300-10,000 h”1. Reaktionstemperaturen vælges inden for et område på 240-390°C, men det foretrækkes i almindelighed at udføre reaktionen ved 270-340°C. Et af de fremtrædende karakteristiske træk ved opfindelsen er, at oxidationsreaktionen kan udføres ved en så lav temperatur.The oxidation reaction is carried out under pressure from atmospheric pressure to several atmospheres. The space velocity of the feed gas varies depending on the reaction temperature and pressure, but it is generally preferred that the gaseous starting mixture be supplied at a space velocity of 300-10,000 h ”1. The reaction temperature is selected within a range of 240-390 ° C, but it is generally preferred to carry out the reaction at 270-340 ° C. One of the prominent features of the invention is that the oxidation reaction can be carried out at such a low temperature.

Fremgangsmåden ifølge opfindelsen belyses nærmere ved de følgende eksempler. I disse eksempler er alle "dele" beregnet på vægt, og selektiviteten til den umættede carboxylsyre er udtrykt ved procentforholdet af mængden (mol) af den dannede umættede carboxylsyre i forhold til mængden (mol) af det omsatte umættede aldehyd. Reaktionstiden måltes fra det tidspunkt, hvor de i eksemplerne beskrevne reaktionsbetingelser faktisk blev etableret.The process according to the invention is illustrated in more detail by the following examples. In these examples, all "portions" are by weight and the selectivity to the unsaturated carboxylic acid is expressed by the percent ratio of the amount (mole) of the unsaturated carboxylic acid formed to the amount (mole) of the unsaturated aldehyde reacted. The reaction time was measured from the time when the reaction conditions described in the examples were actually established.

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EKSEMPEL 1 177 dele ammoniumparamolybdat blev oplyst i 500 dele rent vand holdt ved ca. 60°C, og der sattes 9,6 dele 85% phosphorsyre og 10,5 dele af en 50% vandig opløsning af arsensyre til den ovennævnte opløsning. Derpå sattes en opløsning af 4,88 dele ammonium-metavanadat i 150 dele vand til den ovenstående blanding. Den resulterende blandede opløsning blev underkastet inddampning til tørhed ved opvarmning under omrøring, og det resulterende faste stof blev tørret ved 150°C i 16 timer. Det tørrede faste stof blev pulveriseret i en kuglemølle, trykstøbt, anbragt i en elektrisk ovn og varmebehandlet. Varmebehandlingen udførtes ved hævning af temperaturen fra 100°C til 400°C med en hastighed på 20°C pr. time og bevarelse af det faste stof ved 400°C i 16 timer. Den således opnåede katalysator indeholdt phosphor- og metalkomponenterne i det følgende atomforhold:EXAMPLE 1 177 parts of ammonium paramolybdate were disclosed in 500 parts of pure water held at ca. 60 ° C and 9.6 parts of 85% phosphoric acid and 10.5 parts of a 50% aqueous solution of arsenic acid were added to the above solution. Then a solution of 4.88 parts of ammonium metavanadate in 150 parts of water was added to the above mixture. The resulting mixed solution was subjected to evaporation to dryness by heating with stirring, and the resulting solid was dried at 150 ° C for 16 hours. The dried solid was pulverized in a ball mill, die-cast, placed in an electric oven and heat treated. The heat treatment was carried out by raising the temperature from 100 ° C to 400 ° C at a rate of 20 ° C per minute. hour and maintaining the solid at 400 ° C for 16 hours. The catalyst thus obtained contained the phosphorus and metal components in the following atomic ratio:

MolP0,083As0,037V0,042 0,078MolP0.083As0.037V0.042 0.078

Denne katalysator blev pakket i en reaktionsbeholder af typen med fast leje og holdt ved 295°C, og der indførtes en gasformig blanding bestående af 5 volumen% methacrolein, 5 volumen% oxygen, 20 volumen% damp og 70 volumen% nitrogen i reaktionsbeholderen med en rumhastighed på 2 000 h . Under de ovenstående betingelser udførtes reaktionen i lang tid. Med foreskrevne intervaller blev der udtaget prøver af den fra reaktionsbeholderen udtømte reaktionsgas, som blev analyseret ved gaschromatografi eller lignende for at undersøge katalysatorens aktivitet. Resultaterne er anført i tabel 1.This catalyst was packed in a solid-bed type reaction vessel and maintained at 295 ° C, and a gaseous mixture consisting of 5 volume% methacrolein, 5 volume% oxygen, 20 volume% vapor and 70 volume% nitrogen was introduced into the reaction vessel. space velocity of 2,000 h. Under the above conditions, the reaction was carried out for a long time. At prescribed intervals, samples of the reaction gas discharged from the reaction vessel were collected, which were analyzed by gas chromatography or the like to examine the activity of the catalyst. The results are listed in Table 1.

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Tabel 1Table 1

Reaktionstid Omsætning af Selektivitet til methacrolein methacrylsyre (timer)_ (#) (#) _ 4 57,1 84,9 240 58,0 85,2 480 57,7 85,5 960 57,5 85,8 1440 55,9 85,0 'EKSEMPEL 2Reaction Time Reaction of Selectivity to Methacrolein Methacrylic Acid (Hours) _ (#) (#) _ 4 57.1 84.9 240 58.0 85.2 480 57.7 85.5 960 57.5 85.8 1440 55.9 EXAMPLE 2

En oxidation af acrolein udførtes under anvendelse af den i eksempel 1 fremstillede katalysator. Den gasformige udgangsblanding bestod af 5 volumen# acrolein, 5 volumen# oxygen, 20 volumen# damp og 70 volumen# nitrogen. Reaktionstemperaturen blev indstillet til 300°C. De øvrige arbejdsprocedurer og -betingelser var de samme som i eksempel 1. Resultaterne af forsøget er sammenfattet i tabel 2.An oxidation of acrolein was carried out using the catalyst prepared in Example 1. The gaseous starting mixture consisted of 5 volume # acrolein, 5 volume # oxygen, 20 volume # steam and 70 volume # nitrogen. The reaction temperature was set to 300 ° C. The other working procedures and conditions were the same as in Example 1. The results of the experiment are summarized in Table 2.

Tabel 2Table 2

Reaktionstid Omsætning af Selektivitet til acrolein acrylsyre (timer) (#)_ (#) _ 4 55,3 86,9 240 56,1 87,2 480 55,9 87,5 960 56,0 87,0 1440 55,1 86,7 EKSEMPEL 5Reaction Time Reaction of Selectivity to Acrolein Acrylic Acid (Hours) (#) _ (#) _ 4 55.3 86.9 240 56.1 87.2 480 55.9 87.5 960 56.0 87.0 1440 55.1 86.7 EXAMPLE 5

En katalysator blev fremstillet på samme måde som i eksempel 1, undtagen at den vandige arsensyreopløsning blev ændret til 4,95 dele arsensyrlinganhydrid, at den vandige opløsning af ammonium-metavanadat blev ændret til en opløsning af 3,37 dele ferrinitrat i 50 dele vand, og at varmebehandlingsbetingelserne blev ændret 9A catalyst was prepared in the same manner as in Example 1, except that the aqueous arsenic acid solution was changed to 4.95 parts of arsenic acid anhydride, the aqueous solution of ammonium metavanadate was changed to a solution of 3.37 parts of ferric nitrate in 50 parts of water. and that the heat treatment conditions were changed 9

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således, at maksimumstemperaturen var 380°C, og det tidsrum, hvori denne maksimumstemperatur hlev opretholdt, var 24 timer. Atomforholdet mellem phosphoret og metalkomponenterne i den resulterende katalysator var som følger:so that the maximum temperature was 380 ° C and the time during which this maximum temperature was maintained was 24 hours. The atomic ratio of the phosphorus to the metal components of the resulting catalyst was as follows:

MolP0,083As0,05Fe0,0083 ^4^ 0,125MolP0.083As0.05Fe0.0083 ^ 4 ^ 0.125

Ved anvendelse af den således opnåede katalysator udførtes en oxidation af methacrolein under de samme betingelser som i eksempel 1, undtagen at reaktionstemperaturen blev ændret til 305°C hvorved der blev opnået de i tabel 3 anførte resultater.Using the catalyst thus obtained, an oxidation of methacrolein was carried out under the same conditions as in Example 1, except that the reaction temperature was changed to 305 ° C to obtain the results given in Table 3.

Tabel 3Table 3

Reaktionstid Omsætning af Selektivitet til methacrolein methacrylsyre (timer)_ _[2iL_ _iÉ_ 4 48,9 84,0 240 50,2 86,3 480 50,0 86,5 960 50,1 86,0 EKSEMPEL 4-7Reaction Time Reaction of Selectivity to Methacrolein Methacrylic Acid (Hours) _ _ [2iL_ _iÉ_ 4 48.9 84.0 240 50.2 86.3 480 50.0 86.5 960 50.1 86.0 EXAMPLES 4-7

Der fremstilledes katalysatorer på samme måde som i eksempel 1, undtagen at det i eksempel 1 anvendte ammoniummetavanadat blev ændret til ammoniumparawolframat eller mangannitrat, og i nogle eksempler af den tilsatte mængde arsensyre, den maksimale varmebehandlingstemperatur og/eller det tidsrum, hvori den maksimale temperatur opretholdtes, blev ændret som angivet i tabel 4 nedenfor.Catalysts were prepared in the same manner as in Example 1, except that the ammonium metavanadate used in Example 1 was changed to ammonium parawolframate or manganese nitrate, and in some examples the amount of arsenic acid added, the maximum heat treatment temperature, and / or the period during which the maximum temperature was maintained. , was modified as indicated in Table 4 below.

Ved anvendelse af de således fremstillede katalysatorer udførtes en oxidation af methagroléin eller acrolein under de samme betingelser som i eksempel 1 eller 2, undtagen at reaktionstemperaturen blev ændret som angivet i tabel 4.Using the catalysts thus prepared, oxidation of methagrolene or acrolein was carried out under the same conditions as in Example 1 or 2, except that the reaction temperature was changed as indicated in Table 4.

Katalysatorer, reaktionsbetingelser og forsøgsresultater er sammenfattet i tabel 4.Catalysts, reaction conditions and test results are summarized in Table 4.

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EKSEMPEL 8 11 204 dele phosphormolybdensyre (P20^· 24Mo0^*72H20) opløstes i 500 dele rent vand, og der sattes 4,8 dele arsensyrlinganhydrid til opløsningen. Derpå blev der yderligere sat 75,0 dele fint pulver af stannioxidtil opløsningen. Under omrøring blev der i den resulterende suspension inkorporeret 150 dele 28% vandig ammoniak, og den resulterende blanding blev inddampet til tørhed ved opvarmning. De efterfølgende procedurer blev udført på samme måde som i eksempel 1, og i det afsluttende trin . blev varmebehandlingen udført ved 400°C i 16 timer til opnåelse af en katalysator. Atomforholdet mellem phosphoret og metalkomponenterne i den resulterende katalysator var som følger:EXAMPLE 8 11 204 parts of phosphoric molybdic acid (P 2 O 2 · 24 MoO 2 Then 75.0 parts of fine powder of stannic oxide was added to the solution. With stirring, 150 parts of 28% aqueous ammonia was incorporated into the resulting suspension and the resulting mixture was evaporated to dryness by heating. The following procedures were performed in the same manner as in Example 1, and in the final step. For example, the heat treatment was carried out at 400 ° C for 16 hours to obtain a catalyst. The atomic ratio of the phosphorus to the metal components of the resulting catalyst was as follows:

MolP0,083As0,049Sn0,5 ^rø4^ 0,062MolP0.083As0.049Sn0.5 ^ tube4 ^ 0.062

Ved anvendelse af disse katalysatorer blev der udført en oxidation af methacrolein under de samme betingelser som i eksempel 1, undtagen at reaktionstemperaturen blev ændret til 320°C, hvorved der blev opnået de i tabel 5 anførte resultater.Using these catalysts, oxidation of methacrolein was carried out under the same conditions as in Example 1, except that the reaction temperature was changed to 320 ° C to obtain the results set out in Table 5.

Tabel 5Table 5

Reaktionstid Omsætning af Selektivitet til methacrolein methacrylsyre (timer) (%) (%)_ 4 78,9 84,1 480 81,3 85,2 960 81,1 85,6 EKSEMPEL 9Reaction Time Reaction of Selectivity to Methacrolein Methacrylic Acid (Hours) (%) (%) 4 78.9 84.1 480 81.3 85.2 960 81.1 85.6 Example 9

Ved anvendelse af den i eksempel 8 fremstillede katalysator udførtes en oxidation af acrolein under de samme betingelser som i eksempel 2, undtagen at reaktionstemperaturen blev ændret til 325°C, hvorved der blev opnået de i tabel 6 anførte resultater.Using the catalyst prepared in Example 8, an oxidation of acrolein was carried out under the same conditions as in Example 2, except that the reaction temperature was changed to 325 ° C to obtain the results set forth in Table 6.

DK 155932BDK 155932B

Tabel 6 12Table 6 12

Reaktionstid Omsætning af Selektivitet til acrolein acrylsyre (timer) (%) _ . (%) _ 4 83,4 85,9 480 83,2 86,2 960 84,0 86,0 EKSEMPEL 10 - 12Reaction time Reaction of Selectivity to acrolein acrylic acid (hours) (%) _. (%) 4 83.4 85.9 480 83.2 86.2 960 84.0 86.0 EXAMPLES 10 - 12

Der fremstilledes katalysatorer på samme måde som i eksempel 1, undtagen at den tilsatte mængde ammonium-metavanadat blev ændret til 2,94 dele, og at der efter tilsætningen af ammonium-meta-vanadat yderligere : tilsattes 3,37 dele ferrinitrat, 2,24 dele ammonium-parawolframat eller 23,1 dele mangannitrat i 50 dele rent vand.Catalysts were prepared in the same manner as in Example 1 except that the added amount of ammonium metavanadate was changed to 2.94 parts and that after the addition of ammonium meta-vanadate, further: 3.37 parts of ferric nitrate, 2.24 were added. parts of ammonium parawolframate or 23.1 parts of manganese nitrate in 50 parts of pure water.

Ved anvendelse af de således fremstillede katalysatorer udførtes en oxidation af methacrolein under de samme betingelser som i eksempel 1, undtagen at reaktionstemperaturen blev ændret som angivet i den nedenstående tabel 7.Using the catalysts thus prepared, oxidation of methacrolein was carried out under the same conditions as in Example 1, except that the reaction temperature was changed as indicated in Table 7 below.

Katalysatorer, reaktionsbetingelser og forsøgsresultater er sammenfattet i tabel 7.Catalysts, reaction conditions and test results are summarized in Table 7.

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14 DK 155932 B14 DK 155932 B

Der fremstilledes katalysatorer på samme måde som i eksempel 1, undtagen at det i eksempel 1 anvendte ammonium-metavanadat blev ændret til ammonium-parawolframat, og at der efter tilsætningen af ammonium-parawolframat yderligere tilsattes en vandig opløsning af et nitrat af kobber, jern eller mangan. Atomforholdet for arsen og varmebehandlingsbetingelserne blev ændret noget som angivet i den nedenstående tabel 8.Catalysts were prepared in the same manner as in Example 1, except that the ammonium metavanadate used in Example 1 was changed to ammonium parawolframate and that, after the addition of ammonium parawolframate, an aqueous solution of a copper, iron or nitrate solution was further added. manganese. The atomic ratio of arsenic and heat treatment conditions was changed somewhat as indicated in Table 8 below.

Ved anvendelse af den således fremstillede katalysator udførtes en oxidation af methacrolein eller acrolein under de samme betingelser som i eksempel 1 eller 2, undtagen at reaktionstemperaturen blev ændret som angivet i tabel 8.Using the catalyst thus prepared, oxidation of methacrolein or acrolein was carried out under the same conditions as in Example 1 or 2, except that the reaction temperature was changed as indicated in Table 8.

Katalysatorer, oxidationsbetingelser og resultater er sammenfattet i tabel 8.Catalysts, oxidation conditions and results are summarized in Table 8.

15 DK 155932 BDK 155932 B

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16 DK 155932B16 DK 155932B

EKSEMPEL 18 - 21 204 dele phosphormolybdensyre blev opløst i 500 dele rent vand, og der tilsattes 28,2 dele af en 30% vandig opløsning af arsensyre. Derpå sattes en opløsning af 10,1 dele ferrinitrat i 50 dele rent vand til den ovenstående opløsning, og der tilsattes yderligere 25,0 dele fint pulver af stannioxid. Under omrøring blev der i den resulterende suspension inkorporeret 150 dele 28% vandig ammoniak, og blandingen blev inddampet til tørhed ved opvarmning. De efterfølgende procedurer udførtes på samme måde som beskrevet i eksempel 1, og i det afsluttende trin blev varmebehandlingen udført, ved 400°C i 5 timer, hvorved der blev opnået en katalysator indeholdende jern og tin.EXAMPLES 18 - 21 204 parts of phosphoric molybdic acid were dissolved in 500 parts of pure water and 28.2 parts of a 30% aqueous solution of arsenic acid were added. Then, a solution of 10.1 parts of ferric nitrate in 50 parts of pure water was added to the above solution and an additional 25.0 parts of fine powder of stannic oxide was added. With stirring, 150 parts of 28% aqueous ammonia was incorporated into the resulting suspension and the mixture was evaporated to dryness by heating. The subsequent procedures were carried out in the same manner as described in Example 1, and in the final step the heat treatment was carried out, at 400 ° C for 5 hours, to obtain a catalyst containing iron and tin.

Katalysatorer indeholdende tin og wolfram, vanadium eller mangan blev fremstillet på samme måde som ovenfor, undtagen at ferrinitrat blev erstattet med ammonium-parawolframat, ammonium-meta-vanadat eller mangannitrat.Catalysts containing tin and tungsten, vanadium or manganese were prepared in the same way as above except that ferrin nitrate was replaced with ammonium parawolframate, ammonium meta-vanadate or manganese nitrate.

Ved anvendelse af de således fremstillede katalysatorer udførtes en oxidation af methacrolein eller acrolein under de samme betingelser som i eksempel 1 eller 2, midtagen at reaktionstemperaturen blev ændret som angivet i den nedenstående tabel 9.Using the catalysts thus prepared, oxidation of methacrolein or acrolein was carried out under the same conditions as in Example 1 or 2, except that the reaction temperature was changed as given in Table 9 below.

Katalysatorer, oxidationsbetingelser og forsøgsresultater er sammenfattet i tabel 9·Catalysts, oxidation conditions and test results are summarized in Table 9 ·

17 DK 155932 B17 DK 155932 B

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DK 155932 BDK 155932 B

Der fremstilledes katalysatorer på samme måde som i eksempel 1, undtagen at det i eksempel 1 anvendte ammonium-metavanadat blev ersattet af kobbernitrat, og at der efter tilsætning af en vandig opløsning af kobbernitrat yderligere tilsattes en vandig opløsning af lithiumnitrat, natriumnitrat, kaliumnitrat, rubidiumnitrat eller ceasiumnitrat I nogle eksempler blev den tilsatte mængde arsensyre, den maximale varmebehandlingstemperatir og/eller det tidsrum, hvori den maximale temperatur opretholdtes, ændret som angivet i den nedenstående tabel 10.Catalysts were prepared in the same manner as in Example 1, except that the ammonium metavanadate used in Example 1 was replaced by copper nitrate, and after addition of an aqueous solution of copper nitrate, an aqueous solution of lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate was further added. or cesium nitrate In some examples, the amount of arsenic acid added, the maximum heat treatment temperature and / or the period during which the maximum temperature was maintained was changed as indicated in Table 10 below.

Ved anvendelse af de således fremstillede katalysatorer udførtes en oxidation af methacrolein eller acrolein under de samme betingelser som i eksempel 1 eller 2, undtagen at reaktionstemperaturen blev ændret som angivet i tabel 10.Using the catalysts thus prepared, oxidation of methacrolein or acrolein was carried out under the same conditions as in Example 1 or 2, except that the reaction temperature was changed as indicated in Table 10.

Katalysatorer, oxidationsbetingelser og forsøgsresultater er sammenfattet i tabel 10.Catalysts, oxidation conditions and test results are summarized in Table 10.

19 ; DK 155932B19; DK 155932B

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DK 155932BDK 155932B

Samenligningseksempler 1 og 2Comparative Examples 1 and 2

Der fremstilledes en katalysator på same måde som i eksempel 1, undtagen at der slet ikke tilsattes ammonium-metavanadat.A catalyst was prepared in the same manner as in Example 1, except that no ammonium metavanadate was added at all.

Ved anvendelse af den således opnåede katalysator udførtes en oxidation af methacrolein eller acrolein under de samme betingelser som i eksempel 1 eller 2, undtagen at reaktionstemperaturen blev ændret til 300°C.Using the catalyst thus obtained, oxidation of methacrolein or acrolein was carried out under the same conditions as in Example 1 or 2, except that the reaction temperature was changed to 300 ° C.

Resultaterne er samenfattet i tabel 11.The results are summarized in Table 11.

Tabel 11Table 11

Samenlignings- Udgangs- Reaktions- Omsætning Selektivitet ek- aldehyd tid (%) (%) sempel nr.__(timer) _ _ 1 methacrolein 4 55,0 85,5 120 54,6 84,2 240 55,2 85,3 480 52,1 83,7 2 acrolein 4 49,3 87,2 120 48,4 87,0 240 48,7 86,5 480 46,2 86,9Comparative Initial Reaction Reaction Selectivity Ecaldehyde Time (%) (%) Sample No.__ (Hours) _ 1 Methacrolein 4 55.0 85.5 120 54.6 84.2 240 55.2 85.3 480 52.1 83.7 2 Acrolein 4 49.3 87.2 120 48.4 87.0 240 48.7 86.5 480 46.2 86.9

Som det fremgår af de i tabel 11 anførte resultater, blev der med denne samenligningskatalysator iagttaget en tendens til, at omsætningen eller både omsætningen og selektiviteten blev formindsket i nogen grad ved det tidspunkt, hvor der var gået 480 timer fra reaktionens begyndelse. I modsætning hertil blev der, som det fremgår af de i tabel 1-10 anførte resultater, i tilfælde af katalysatorer, hvori der var indført mindst ét metal udvalgt blandt vanadium, wolfram, kobber, jern, mangan og tin, eventuelt samen med et alkalimetalelement, næppe iagttaget en sådan tendens, selv hvis reaktionen udførtes i meget længere tid.As can be seen from the results set forth in Table 11, with this comparison catalyst, the reaction or both the reaction and the selectivity tended to decrease to some extent by the time 480 hours had elapsed from the beginning of the reaction. In contrast, in the case of catalysts in which at least one metal was selected from vanadium, tungsten, copper, iron, manganese and tin, optionally together with an alkali metal element, as shown by the results in Tables 1-10, , hardly observed such a trend, even if the reaction was carried out for a much longer time.

44

Claims (7)

1. Fremgangsmåde til fremstilling af acrylsyre eller methacrylsy-re. ved katalytisk oxidation af acrolein eller methacrolein i gasfasen ved en temperatur på 240 - 390°C med molekylært oxygen, kendetegnet ved, at den katalytiske oxidation udføres i nærvær af en katalysator med en sammensætning repræsenteret ved den følgende almene formel: P MOvAs (NH/),X Yf0 a b c' 4 d efg hvori a, b, c, e, f og g står for et atomforhold for hver komponent idet a er inden for et område på 0,03 - 0,2, b er 1, c er indenfor et område på 0,015 - 0,15, e er indenfor et område på 0,003 - 1, f er indenfor et område på 0 - 0,17, og g har en værdi bestemt ved valensen af de i katalysatoren tilstedeværende elementer, medens d betyder antallet af ammoniumgrupper, som er indenfor et område på 0,01 - 0,3, X betyder mindst ét metal udvalgt blandt vanadium, wolfram, kobber, jern, mangan og tin, og Y betyder mindst ét alkali· metalelement udvalgt blandt lithium, natrium, kalium, rubidium og caesium.A process for preparing acrylic acid or methacrylic acid. by catalytic oxidation of acrolein or methacrolein in the gas phase at a temperature of 240-390 ° C with molecular oxygen, characterized in that the catalytic oxidation is carried out in the presence of a catalyst having a composition represented by the following general formula: P MOvAs (NH ), X Yf0 abc '4 d efg wherein a, b, c, e, f and g represent an atomic ratio for each component with a being within a range of 0.03 - 0.2, b being 1, c being within a range of 0.015 - 0.15, e is within a range of 0.003 - 1, f is within a range of 0 - 0.17, and g has a value determined by the valence of the elements present in the catalyst, while d means the number of ammonium groups within a range of 0.01 - 0.3, X means at least one metal selected from vanadium, tungsten, copper, iron, manganese and tin, and Y means at least one alkali metal element selected from lithium, sodium , potassium, rubidium and cesium. 2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at katalysatoren anvendes i båret tilstand på en bærer.Process according to claim 1, characterized in that the catalyst is used in a supported state on a support. 3. Fremgangsmåde ifølge krav 1, kendetegnet ved, at katalysatoren er varmebehandlet ved en temperatur på 300 - 440°C.Process according to claim 1, characterized in that the catalyst is heat treated at a temperature of 300-440 ° C. 4. Fremgangsmåde ifølge krav 1, kendetegnet ved, at det umættede aldehyd er methacrolein.Process according to claim 1, characterized in that the unsaturated aldehyde is methacrolein. 5. Fremgangsmåde ifølge krav 1, kendetegnet ved, at metallet X er kobber.Process according to claim 1, characterized in that the metal X is copper. 6. Fremgangsmåde ifølge krav 1, kendetegn et ved, at katalysatoren er sammensat af en heteropolysyre af hver metalkomponent og et ammoniumsalt deraf.Process according to claim 1, characterized in that the catalyst is composed of a heteropoly acid of each metal component and an ammonium salt thereof. 22 DK 155932B22 DK 155932B 7. Fremgangsmåde ifølge ethvert af de forudgående krav, kendetegnet ved, at f er indenfor et område på 0,001 - 0,12, og d er indenfor et område på 0,01 - 0,2.Method according to any one of the preceding claims, characterized in that f is within a range of 0.001 - 0.12 and d is within a range of 0.01 - 0.2.
DK436074A 1973-08-16 1974-08-15 METHOD OF PREPARING ACRYLIC ACID OR METHACRYLIC ACID DK155932C (en)

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JP9197673A JPS5529061B2 (en) 1973-08-16 1973-08-16
JP9197673 1973-08-16
FR7337589 1973-10-22
FR7337589A FR2248257B1 (en) 1973-08-16 1973-10-22
GB4935473 1973-10-23
GB4935473A GB1438806A (en) 1973-08-16 1973-10-23 Catalysts and processes using them
NL7314507A NL169067C (en) 1973-08-16 1973-10-23 PROCESS FOR PREPARING UNSATURATED CARBONIC ACIDS AND PROCESS FOR PREPARING AN IDEAL CATALYST.
DE2353131A DE2353131C3 (en) 1973-08-16 1973-10-23 Catalyst for the gas phase oxidation of unsaturated aldehydes to unsaturated carboxylic acids
NL7314507 1973-10-23
DE2353131 1973-10-23

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JPS57297B2 (en) * 1974-01-19 1982-01-06
JPS5946934B2 (en) * 1976-02-09 1984-11-15 東ソー株式会社 Method for manufacturing methacrylic acid
IN147123B (en) * 1976-10-19 1979-11-17 Standard Oil Co Ohio
US4110369A (en) * 1976-10-19 1978-08-29 The Standard Oil Company Process for the preparation of unsaturated acids from unsaturated aldehydes
US4169070A (en) 1978-04-12 1979-09-25 Halcon Research And Development Corporation Catalyst and process for producing unsaturated acids by using same
DE3208572A1 (en) * 1982-03-10 1983-09-22 Basf Ag, 6700 Ludwigshafen METHOD AND CATALYST FOR PRODUCING METHACRYLIC ACID
DE3364798D1 (en) * 1982-04-21 1986-09-04 Bridgestone Tire Co Ltd Use of a catalyst for cleaning exhaust gas particulates
EP0113156B1 (en) * 1983-01-05 1987-03-04 Mitsubishi Rayon Co., Ltd. Process for the calcination of phosphorus-molybdenum catalyst
JPH0791212B2 (en) * 1988-07-11 1995-10-04 三菱レイヨン株式会社 Method for producing methacrylic acid
JP2002322116A (en) 2001-04-25 2002-11-08 Nippon Shokubai Co Ltd Method for producing (meth)acrylic acid

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NL169067C (en) 1982-01-04
SE7410384L (en) 1975-02-17
JPS5529061B2 (en) 1980-07-31
FR2248257B1 (en) 1977-09-09
BE818803A (en) 1974-12-02
NO142217C (en) 1980-07-30
NO142217B (en) 1980-04-08
BR7406751D0 (en) 1975-06-03
DK155932C (en) 1989-10-30
JPS5041811A (en) 1975-04-16
NO742842L (en) 1975-03-17
DE2353131C3 (en) 1980-02-14
IE39880B1 (en) 1979-01-17
DE2353131A1 (en) 1975-04-24
SE412380B (en) 1980-03-03
ES429309A1 (en) 1976-10-01
DK436074A (en) 1975-04-28
IE39880L (en) 1975-02-16
DE2353131B2 (en) 1979-06-13
FR2248257A1 (en) 1975-05-16

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