NO142242B - Oxidation catalyst consisting of oxides or oxide complexes of wolfram, vanadium and molybdenum, especially for use in the production of acrylic acid and methacrylic acid. - Google Patents

Oxidation catalyst consisting of oxides or oxide complexes of wolfram, vanadium and molybdenum, especially for use in the production of acrylic acid and methacrylic acid. Download PDF

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Publication number
NO142242B
NO142242B NO744446A NO744446A NO142242B NO 142242 B NO142242 B NO 142242B NO 744446 A NO744446 A NO 744446A NO 744446 A NO744446 A NO 744446A NO 142242 B NO142242 B NO 142242B
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Prior art keywords
molybdenum
catalyst according
acrylic acid
production
vanadium
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NO744446A
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Norwegian (no)
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NO744446L (en
NO142242C (en
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Serge Roman Dolhyji
Ernest Carl Milberger
Noel Jerome Bremer
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Standard Oil Co Ohio
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Publication of NO142242C publication Critical patent/NO142242C/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts 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
    • B01J23/84—Catalysts 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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Description

Den foreliggende oppfinnelse angår en oksydasjonskatalysator bestående av oksyder eller oksydkomplekser av wolfram, vanadium og molybden, særlig til bruk ved fremstilling av akrylsyre og metakrylsyre og eventuelt inneholdende ett eller flere av elementene Fe, Co, Ni, Zn, Mg, Mn, Cu, Bi, Ti, The present invention relates to an oxidation catalyst consisting of oxides or oxide complexes of tungsten, vanadium and molybdenum, particularly for use in the production of acrylic acid and methacrylic acid and optionally containing one or more of the elements Fe, Co, Ni, Zn, Mg, Mn, Cu, Bi , Ten,

Zr, Sn, P, et alkalimetall, et jordalkalimetall, lantan eller Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum or

et element fra lantanid-gruppen. Oppfinnelsen og foretrukne utførelsesformer av den går frem av patentkravene. an element from the lanthanide group. The invention and preferred embodiments thereof are set forth in the patent claims.

Katalysatorer som ligner katalysatoren ifølge oppfinnelsen, er kjent, se US-patent nr. 3 567 772, som be- Catalysts similar to the catalyst according to the invention are known, see US Patent No. 3,567,772, which

skriver katalysatorer inneholdende WVMo. I tillegg hertil inneholder katalysatoren ifølge oppfinnelsen uran og/eller torium, hvorved det uventet oppnås katalysatorer som med for- writes catalysts containing WVMo. In addition to this, the catalyst according to the invention contains uranium and/or thorium, whereby catalysts are unexpectedly obtained which with

del kan brukes ved fremstilling av akrylsyre og metakrylsyre. part can be used in the production of acrylic acid and methacrylic acid.

Det er kjent å fremstille akrylsyre ved oksyda- It is known to produce acrylic acid by oxidizing

sjon av akrolein og metakrylsyre ved oksydasjon av metakrolein. tion of acrolein and methacrylic acid by oxidation of methacrolein.

Ved anvendelse av katalysatoren ifølge oppfinnelsen isteden- When using the catalyst according to the invention instead of

for de tidligere kjente katalysatorer oppnås imidlertid særlig gode resultater, hvilket vil bli vist nedenfor. for the previously known catalysts, however, particularly good results are obtained, which will be shown below.

Selv om katalysatoren ifølge oppfinnelsen er sær- Although the catalyst according to the invention is particularly

lig effektiv for fremstilling av akrylsyre ut fra akrolein og fremstilling av metakrylsyre ut fra metakrolein, så er dog katalysatoren ifølge oppfinnelsen også meget effektiv for oksydasjonsreaksjoner såsom oksydasjon av butadien til rnalein-syreanhydrid og den oksydative forestring av umettede alde- equally effective for the production of acrylic acid from acrolein and the production of methacrylic acid from methacrolein, however, the catalyst according to the invention is also very effective for oxidation reactions such as the oxidation of butadiene to rnaleic anhydride and the oxidative esterification of unsaturated aldehydes

hyder til de tilsvarende umettede estere. Katalysatoren ifølge oppfinnelsen er også meget reaktiv og er istand til å bevirke en meget selektiv oksydasjon av akrolein til akrylsyre ved lave temperaturer under dannelse av lite eller ingen eddiksyre. hyder to the corresponding unsaturated esters. The catalyst according to the invention is also very reactive and is capable of effecting a very selective oxidation of acrolein to acrylic acid at low temperatures with the formation of little or no acetic acid.

Som nevnt ovenfor er det kjent katalysatorer As mentioned above, catalysts are known

som har meget til felles med katalysatoren ifølge oppfinnelsen, se for eksempel US-patent nr. 3 567 772. Videre er katalysatorer av den her nevnte generelle type kjent, og en fagmann på området behøver ikke mer enn en beskrivelse av elementene i katalysatoren ifølge oppfinnelsen for å kunne fremstille den. which has much in common with the catalyst according to the invention, see for example US patent no. 3 567 772. Furthermore, catalysts of the general type mentioned here are known, and a person skilled in the field does not need more than a description of the elements in the catalyst according to the invention in order to produce it.

Normalt blir katalysatoren ifølge oppfinnelsen fremstilt ved. at man blander katalysatoringrediensene i riktig forhold i en vandig blanding, tørrer den resulterende vandige dispersjon og kalsinerer produktet. De ingredienser som inngår ved fremstillingen av katalysatoren, kan være oksyder, halogenide: nitrater eller andre salter av den spesielle forbindelse som tilsettes. Hvis det anvendes en bærer, blir det materiale som inneholder bæreren, vanligvis inkorporert i katalysatoren sammen med de andre ingrediensene. Etter at katalysatoringrediensene er bragt sammen og en vandig dispersjon fremstilt, inndampes denne til tørrhet, og det tørrede faste stoff oppvarmes i nærvær av luft ved temperaturer mellom ca. 200 og 600°C. Denne kalsinering skjer utenfor katalysator-reaktoren, eller man kan benytte aktivering in situ. Normally, the catalyst according to the invention is produced by that one mixes the catalyst ingredients in the correct ratio in an aqueous mixture, dries the resulting aqueous dispersion and calcines the product. The ingredients included in the production of the catalyst can be oxides, halides: nitrates or other salts of the particular compound that is added. If a carrier is used, the material containing the carrier is usually incorporated into the catalyst along with the other ingredients. After the catalyst ingredients have been brought together and an aqueous dispersion prepared, this is evaporated to dryness, and the dried solid is heated in the presence of air at temperatures between approx. 200 and 600°C. This calcination takes place outside the catalyst reactor, or activation in situ can be used.

En rekke preparater kunne benyttes ved fremstilling av ønskede katalysatorer ifølge oppfinnelsen, men man foretrekker katalysatorer som inneholder molybden i en delvis redusert til-stand lavere enn seksverdig molybden. Fremstillingen av katalysatorer ifølge oppfinnelsen inneholdende redusert molybden er beskrevet nedenfor under spesielle utførelsesformer. A number of preparations could be used in the production of desired catalysts according to the invention, but catalysts containing molybdenum in a partially reduced state lower than hexavalent molybdenum are preferred. The production of catalysts according to the invention containing reduced molybdenum is described below under special embodiments.

Hovedtrekkene ved katalysatoren ifølge oppfinnelsen er angitt ovenfor. Med hensyn til sammensetningen er det visse foretrukne utførelsesformer. Man foretrekker de katalysatorer i hvilke mer enn ca. 50 % av atomene, eksklusive oksygen og eventuelt bæremateriale, er molybden. Videre foretrekker man de katalysatorer som ikke inneholder noen av de valgfrie komponenter eller de eventuelt tilstedeværende bestanddeler Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu eller blandinger derav. The main features of the catalyst according to the invention are indicated above. With respect to the composition, there are certain preferred embodiments. One prefers those catalysts in which more than approx. 50% of the atoms, excluding oxygen and any carrier material, are molybdenum. Furthermore, those catalysts which do not contain any of the optional components or the possibly present components Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu or mixtures thereof are preferred.

Katalysatoren ifølge oppfinnelsen kan beskrives ved hjelp av den følgende empiriske formel: The catalyst according to the invention can be described using the following empirical formula:

A D, W V, Mo 0 A D, W V, Mo 0

a b c d ex a b c d ex

hvor A er Co, Ni, Zn, Cu, Mg, Mn, Bi, Fe, where A is Co, Ni, Zn, Cu, Mg, Mn, Bi, Fe,

Ti, Zr, Sn, P, et alkalimetall, et jordalkalimetall, lantan, et element fra lantanid-gruppen eller blanding derav; og Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum, an element from the lanthanide group or mixture thereof; and

D er uran, torium eller blanding derav. D is uranium, thorium or a mixture thereof.

En foretrukken katalysator som inneholder valgfrie elementer, har den empiriske formel A preferred catalyst containing optional elements has the empirical formula

A D, W V, Mo 0 A D, W V, Mo 0

a b c d e x a b c d e x

hvor A representerer Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu, eller blanding derav og where A represents Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu, or a mixture thereof and

D er uran, torium eller en blanding derav; D is uranium, thorium or a mixture thereof;

og hvor a er større enn 0 og høyst 5; and where a is greater than 0 and at most 5;

b, c og d er 0,1 til 10; b, c and d are 0.1 to 10;

e er et tall på 6 til 16; og e is a number from 6 to 16; and

x er det antall oksygenatomer som er nødvendig for x is the number of oxygen atoms required for

å tilfredsstille valensene av de andre tilstedeværende elementer. to satisfy the valences of the other elements present.

I tillegg til de aktive katalytiske ingredienser kan katalysatoren ifølge oppfinnelsen inneholde et bærermateriale. Egnede bærematerialer innbefatter silisiumdioksyd, aluminiumoksyd, zirkoniumdioksyd, titandioksyd, silisiumkarbid, borfosfat og lignende. Et foretrukket bæremateriale er siliszumdioksyd. In addition to the active catalytic ingredients, the catalyst according to the invention can contain a carrier material. Suitable carrier materials include silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, silicon carbide, boron phosphate and the like. A preferred carrier material is silicon dioxide.

Som nevnt ovenfor er katalysatoren ifølge oppfinnelsen egnet til bruk i en rekke forskjellige oksydasjonsreaksjoner. Foretrukne reaksjoner er i denne forbindelse fremstillingen av umettede syrer ut fra de tilsvarende umettede aldehyder. Ved en slik prosess fremstilles akrylsyre eller metakrylsyre ved omsetning av akrolein eller metakrolein med molekylært oksygen i nærvær av vanndamp ved temperaturer mellom 200 og 500°C. Av spesiell interesse er fremstillingen av akrylsyre fra akrolein, idet man da oppnår ytterst fordelaktige resultater. As mentioned above, the catalyst according to the invention is suitable for use in a number of different oxidation reactions. Preferred reactions in this connection are the preparation of unsaturated acids from the corresponding unsaturated aldehydes. In such a process, acrylic acid or methacrylic acid is produced by reacting acrolein or methacrolein with molecular oxygen in the presence of steam at temperatures between 200 and 500°C. Of particular interest is the production of acrylic acid from acrolein, as extremely advantageous results are then obtained.

Den kjente prosess utføres ved at det umettede aldehyd bringes i kontakt med molekylært oksygen i nærvær av vanndamp ved en temperatur mellom 200 og 500°C. Forholdet mellom reaktantene kan variere innenfor vide grenser, men normalt anvendes et mol-forhold mellom molekylært oksygen og aldehyd på ca. 0,5 til ca. 5 mol. Molekylært oksygen anvendes hensikts-messig i form av luft. Mengden av vanndamp kan variere innen vide grenser, fra den lille mengde som utvikles under reaksjonen til 20 mol vanndamp pr. mol aldehyd eller mer. Ifølge den foretrukne utførelsesform blir ca. 1 til ca. 10 mol vanndamp tilsatt til utgangsmaterialet. The known process is carried out by bringing the unsaturated aldehyde into contact with molecular oxygen in the presence of steam at a temperature between 200 and 500°C. The ratio between the reactants can vary within wide limits, but normally a molar ratio between molecular oxygen and aldehyde of approx. 0.5 to approx. 5 mol. Molecular oxygen is suitably used in the form of air. The amount of water vapor can vary within wide limits, from the small amount that develops during the reaction to 20 mol of water vapor per moles of aldehyde or more. According to the preferred embodiment, approx. 1 to approx. 10 moles of water vapor added to the starting material.

Reaksjonen kan utføres i et stasjonært sjikt eller et hyirvelsjikt under anvendelse av atmosfærisk, overatmosfærisk eller underatmosfærisk trykk. Den tilsynelatende kontakttid kan variere betydelig, men normalt anvendes kontakttider fra en brøkdel av et sekund til 20 sekunder eller mer. The reaction can be carried out in a stationary bed or a fluidized bed using atmospheric, superatmospheric or subatmospheric pressure. The apparent contact time can vary considerably, but normally contact times from a fraction of a second to 20 seconds or more are used.

Under anvendelse av katalysatoren ifølge oppfinnelsen oppnåes et meget godt utbytte av umettet syre ved lave temperaturer, med liten eller ingen dannelse av eddiksyre. Using the catalyst according to the invention, a very good yield of unsaturated acid is achieved at low temperatures, with little or no formation of acetic acid.

Sammenligningseksempel A og eksempler 1- 3. Comparative example A and examples 1-3.

Sammenligning mellom.katalysatoren ifølge oppfinnelsen og kjente katalysatorer. Comparison between the catalyst according to the invention and known catalysts.

Det ble fremstilt en katalysator ifølge oppfinnelsen, og denne ble sammenlignet med en katalysator som beskrevet i US-patent nr. 3 567 773. Katalysatorene ble fremstilt som følger: A catalyst according to the invention was prepared, and this was compared with a catalyst as described in US patent no. 3,567,773. The catalysts were prepared as follows:

Sammenligningseksempel A Comparative example A

62 % W1 2V3Mol2°x og 38 % Si02* Denne katalysa- 62% W1 2V3Mol2°x and 38% SiO2* This catalysis

tor ble fremstilt som angitt i eksempel 6 i US-patent nr. ---3 5,67 773. r-^-w-c. tor was prepared as set forth in Example 6 of US Patent No. ---3 5.67 773. r-^-w-c.

Eksempler 1- 3 Examples 1-3

U2W1 2V3Mo12°x" Det k^ e fremstilt en dispersjon U2W1 2V3Mo12°x" A dispersion can be prepared

i 500 ml destillert vann. Dispersjonen inneholdt 72,0 g MoO^, 11,36 g ^ 2Q5 °9 9,19 g wolfram-metall i pulverform. Dispersjonen ble oppvarmet under tilbakeløp i 2 timer, hvorunder dispersjonens farve forandret seg til blåsort. in 500 ml of distilled water. The dispersion contained 72.0 g MoO^, 11.36 g ^ 2Q5 °9 9.19 g tungsten metal in powder form. The dispersion was heated under reflux for 2 hours, during which the color of the dispersion changed to blue-black.

35,3 g U02(C2H302)2.2H20 ble separat oppløst i vann og tilsatt til dispersjonen. Den resulterende blanding ble oppvarmet under tilbakeløp i 1 time og deretter inndampet til et pasta-materiale. Pastaen ble tørret i en ovn ved 110°C 35.3 g of UO 2 (C 2 H 3 O 2 ) 2.2H 2 O were separately dissolved in water and added to the dispersion. The resulting mixture was heated under reflux for 1 hour and then evaporated to a paste material. The paste was dried in an oven at 110°C

natten over. Katalysatoren ble malt og siktet, hvorved man fikk en porsjon omfattende størrelser på 10-30 mesh. overnight. The catalyst was ground and sieved, whereby a portion comprising sizes of 10-30 mesh was obtained.

De ovenfor fremstilte katalysatorer ble plassert The catalysts prepared above were placed

i en reaktor bygget av et rør av rustfritt stål med innvendig diameter og 1,0 cm og med en reaksjonssone på 20 ml. Katalysatoren ifølge oppfinnelsen ble aktivert i 2 timer i en luftstrøm ved 400°C. Reaktoren ble matet med en blanding av akrolein, in a reactor built from a stainless steel tube with an internal diameter of 1.0 cm and with a reaction zone of 20 ml. The catalyst according to the invention was activated for 2 hours in an air stream at 400°C. The reactor was fed with a mixture of acrolein,

luft og vanndamp i mol-forholdet 1:10:6. Temperaturen av den air and water vapor in the mole ratio 1:10:6. The temperature of it

omgivende varmeblokk og den tilsynelatende kontakttid er angitt i tabell I. Videre er resultatene angitt i tabell I under anvendelse av de følgende definisjoner: ambient heat block and the apparent contact time are given in Table I. Furthermore, the results are given in Table I using the following definitions:

Eksempel 4 Example 4

En katalysator med sammensetningen Mo^2 V3 w^ 2 Sn0 5 U0 5 °x (Nr" 6139-1"4) ble 1 en mengde på ca. 20 % påført alundumkuler som et overtrekk. A catalyst with the composition Mo^2 V3 w^ 2 Sn0 5 U0 5 °x (Nr" 6139-1"4) was 1 a quantity of approx. 20% applied alundum beads as a coating.

Oksydasjonen av akrolein til akrylsyre ble utført The oxidation of acrolein to acrylic acid was carried out

i en 20 cm<3> reaktor med stasjonært sjikt under anvendelse av et molart tilførselsforhold mellom akrolein, luft, N2 og E^ O på 1:8,5:2,5:6, en kontakttid på 1,94 sekund og en reaktortempera- in a 20 cm<3> fixed bed reactor using a molar feed ratio of acrolein, air, N2 and E^O of 1:8.5:2.5:6, a contact time of 1.94 seconds and a reactor temp. -

tur på 288°C. Omdannelsen til akrylsyre pr= passasje var 91,1 %. Den samlede omdannelse var 98,8 %, og selektiviteten til akrylsyre var 92,3 %. trip at 288°C. The conversion to acrylic acid per passage was 91.1%. The overall conversion was 98.8%, and the selectivity to acrylic acid was 92.3%.

Eksempel 5 Example 5

En katalysator med sammensetningen Mo^2 V3 w^ 2A catalyst with the composition Mo^2 V3 w^ 2

Th2 0x ble anvendt ved oksydasjonen av akrolein til akrylsyre, Th2 0x was used in the oxidation of acrolein to acrylic acid,

hvor molforholdet akrolein:luft:Ho0 var 1:10:6, kontakttiden 2,2 sekunder og reaksjonstemperaturen 232 C. Dette ga en samlet omdannelse på 95,6 %, en omdannelse til akrylsyre pr. passasje på 87,1 % og en selektivitet til akrylsyre på 91,1 %. where the molar ratio acrolein:air:Ho0 was 1:10:6, the contact time 2.2 seconds and the reaction temperature 232 C. This gave a total conversion of 95.6%, a conversion to acrylic acid per passage of 87.1% and a selectivity to acrylic acid of 91.1%.

På samme måte som vist ved eksemplene ovenfor In the same way as shown by the examples above

anvendes andre katalysatorer ifølge oppfinnelsen som inneholder torium og/eller uran, eller som inneholder forskjellige mengder uran eller torium og forskjellige valgfrie elementer, other catalysts according to the invention are used which contain thorium and/or uranium, or which contain different amounts of uranium or thorium and different optional elements,

såsom Fe, Mn, Ni, Mg og lignende, for fremstilling av akryl- such as Fe, Mn, Ni, Mg and the like, for the production of acrylic

syre. Videre anvendes aktiverte katalysatorer inneholdende forskjellige mengder wolfram, vanadium og molybden. acid. Activated catalysts containing different amounts of tungsten, vanadium and molybdenum are also used.

Ved hjelp av katalysatorene ifølge oppfinnelsen fremstilles også maleinsyreanhydrid, metakrylsyre eller akrylater ved forøvrig kjente oksydasjonsreaksjoner. Using the catalysts according to the invention, maleic anhydride, methacrylic acid or acrylates are also produced by otherwise known oxidation reactions.

Claims (5)

1. Oksydasjonskatalysator bestående av oksyder eller oksydkomplekser av wolfram, vanadium og molybden, særlig til bruk ved fremstilling av akrylsyre og metakrylsyre og eventuelt inneholdende ett eller flere av elementene Fe, Co, Ni, Zn, Mg, Mn, Cu, Bi, Ti, Zr, Sn, P, et alkalimetall, et jord-aikalimetaii, lantan eller et element fra lantanid-gruppen, karakterisert ved at den i tillegg inneholder katalytisk virksomme mengder av uran, torium eller blandinger derav.1. Oxidation catalyst consisting of oxides or oxide complexes of tungsten, vanadium and molybdenum, particularly for use in the production of acrylic acid and methacrylic acid and optionally containing one or more of the elements Fe, Co, Ni, Zn, Mg, Mn, Cu, Bi, Ti, Zr, Sn, P, an alkali metal, an alkaline earth metal, lanthanum or an element from the lanthanide group, characterized in that it also contains catalytically effective amounts of uranium, thorium or mixtures hence. 2. Katalysator ifølge krav 1, karakterisert ved at mer enn ca. 50 % av atomene, eksklusive oksygen og eventuelt bæremateriale, er molybden.2. Catalyst according to claim 1, characterized in that more than approx. 50% of the atoms, excluding oxygen and any carrier material, are molybdenum. 3. Katalysator ifølge krav 1 eller 2, karakterisert ved at den ikke inneholder noen av de valgfrie komponenter.3. Catalyst according to claim 1 or 2, characterized in that it does not contain any of the optional components. 4. Katalysator ifølge krav 1, karakterisert ved at den inneholder Sn.4. Catalyst according to claim 1, characterized in that it contains Sn. 5. Katalysator ifølge krav 1, karakterisert ved at den har den empiriske formel A D, W V, Mo O a b c d e x hvor A representerer Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu, eller blanding derav og D er uran, torium eller en blanding derav; og hvor a er større enn O og høyst 5; b, c og d er 0,1 til 10; e er et tall på 6 til 16; og x er det antall oksygenatomer som er nødvendig for å tilfredsstille valensene av de andre tilstedeværende elementer.5. Catalyst according to claim 1, characterized in that it has the empirical formula A D, W V, Mo O a b c d e x where A represents Fe, Ni, Co, Zn, Sn, Mn, Mg, Cu, or a mixture thereof and D is uranium, thorium or a mixture thereof; and where a is greater than O and at most 5; b, c and d are 0.1 to 10; e is a number from 6 to 16; and x is the number of oxygen atoms necessary to satisfy the valences of the other elements present.
NO744446A 1973-12-26 1974-12-10 Oxidation catalyst consisting of oxides or oxide complexes of wolfram, vanadium and molybdenum, especially for use in the production of acrylic acid and methacrylic acid. NO142242C (en)

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US4301030A (en) 1980-08-05 1981-11-17 The Standard Oil Company Bi-containing methacrolein oxidation catalysts
US4301031A (en) 1980-08-05 1981-11-17 The Standard Oil Company Methacrolein oxidation catalysts
JP2702864B2 (en) * 1993-03-12 1998-01-26 株式会社日本触媒 Catalyst regeneration method
DE10137534A1 (en) 2001-08-01 2003-02-13 Basf Ag Maleic anhydride production useful as an intermediate in the production of e.g. gamma-butyrolactone, comprises the heterogeneous catalyzed gas phase oxidation of n-butene

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IT1045704B (en) * 1973-11-28 1980-06-10 Sir Soc Italiana Resine Spa REFINEMENTS IN THE ACRYLIC ACID PREPARATION PROCEDURE

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CS212754B2 (en) 1982-03-26
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NO744446L (en) 1975-07-21
DE2459092A1 (en) 1975-07-10
IT1027951B (en) 1978-12-20
GB1482686A (en) 1977-08-10
DD115652A5 (en) 1975-10-12
RO66354A (en) 1979-03-15
CH600947A5 (en) 1978-06-30
ATA1028474A (en) 1977-10-15
BG31643A3 (en) 1982-02-15
ES433229A1 (en) 1977-11-01
BE823871A (en) 1975-06-27
NO142242C (en) 1980-07-23
IN143815B (en) 1978-02-11
FR2255953B1 (en) 1981-12-24
AT343604B (en) 1978-06-12
CA1055468A (en) 1979-05-29

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