NO762836L - - Google Patents
Info
- Publication number
- NO762836L NO762836L NO762836A NO762836A NO762836L NO 762836 L NO762836 L NO 762836L NO 762836 A NO762836 A NO 762836A NO 762836 A NO762836 A NO 762836A NO 762836 L NO762836 L NO 762836L
- Authority
- NO
- Norway
- Prior art keywords
- catalyst
- production
- denotes
- molybdenum
- molybdenum trioxide
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 claims description 70
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 16
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 3
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—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
- B01J23/16—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
I US patentskrift nr. 3882047 og japansk patentskriftIn US patent document No. 3882047 and Japanese patent document
nr. 4733082 er beskrevet katalysatorer som er nyttige for anvendelse ved oxydasjon av umettede aldehyder til umettede syrer og som er fremstilt i en vandig oppløsning av fosformolybdensyre. No. 4733082 describes catalysts which are useful for use in the oxidation of unsaturated aldehydes to unsaturated acids and which are prepared in an aqueous solution of phosphormolybdic acid.
I US patentskrift nr. 3882047 er beskrevet katalysatorer avUS patent document no. 3882047 describes catalysts of
molybden, fosfor, minst ett element som tallium, rubidium, cesium og kalium, og minst ettelement som krom, silicium, aluminium, molybdenum, phosphorus, at least one element such as thallium, rubidium, cesium and potassium, and at least one element such as chromium, silicon, aluminium,
jern og titan. I japansk patentskrift nr. 4733082 er beskrevet katalysatorer av molybden, fosfor og minst ettelement som arsen, iron and titanium. Japanese patent document no. 4733082 describes catalysts of molybdenum, phosphorus and at least one element such as arsenic,
bor, silicium, kadmium, bly, wolfram, tallium, indium, germaniumboron, silicon, cadmium, lead, tungsten, thallium, indium, germanium
av of
og tinn. Den foreliggende oppfinnelse er resultatet en under-søkelse for å komme frem til mer effektive katalysatorer for anvendelse ved oxydasjon av acrolein eller methacrolein til hhv. acrylsyre eller methacrylsyre. and tin. The present invention is the result of an investigation to arrive at more effective catalysts for use in the oxidation of acrolein or methacrolein to resp. acrylic acid or methacrylic acid.
Oppfinnelsen angår således en fremgangsmåte ved fremstilling av acrylsyre eller methacrylsyre ved oxydasjo,n av hhv. The invention thus relates to a method for the production of acrylic acid or methacrylic acid by the oxidation of
acrolein eller methacrolein med molekylært oxygen i dampfase ved en reaksjonstemperatur på 200-500°C i nærvær av en oxydkatalysator og eventuelt vanndamp, og fremgangsmåten er særpreget ved at det som katalysator anvendes en katalysator som kan representeres ved den følgende empiriske formel acrolein or methacrolein with molecular oxygen in the vapor phase at a reaction temperature of 200-500°C in the presence of an oxide catalyst and optionally water vapour, and the method is characterized by the fact that a catalyst is used as catalyst which can be represented by the following empirical formula
A Cr, Mo, P O ,A Cr, Mo, P O ,
a b 3 c x'a b 3 c x'
hvori A betegner minst et element bestående av rubidium, tallium, cesium, arsen, titan eller kalium, a betegner et positivt tall på under ca. 3, b betegner et tall fra 0 til ca. 3, c betegner et positivt tall på under ca. 2, og x betegner det antall oxygeri- where A denotes at least one element consisting of rubidium, thallium, cesium, arsenic, titanium or potassium, a denotes a positive number of less than approx. 3, b denotes a number from 0 to approx. 3, c denotes a positive number of less than approx. 2, and x denotes the number of oxygeri-
atomer som er nødvendige på grunn av valenstilstandene for de andre tilstedeværende elementer, og atoms necessary because of the valence states of the other elements present, and
hvori i det minste en del av det for fremstillingen av katalysatoren anvendte molybden tilføres i form av molybdentrioxyd. in which at least part of the molybdenum used for the production of the catalyst is added in the form of molybdenum trioxide.
Uventede forbedringer av utbyttet av acrylsyre og methacrylsyre fås ved anvendelse av de beskrevne katalysatorer, hvor molybdentrioxyd innføres ved fremstillingen av katalysatorene, sammenlignet med de resultater som erholdes med de kjente katalysatorer fremstilt fra fosformolybdensyre. Unexpected improvements in the yield of acrylic acid and methacrylic acid are obtained by using the described catalysts, where molybdenum trioxide is introduced during the production of the catalysts, compared to the results obtained with the known catalysts produced from phosphormolybdic acid.
Det viktigste trekk ved den foreliggende oppfinnelse er fremstillingen av den anvendte katalysator. Innføringen av molybdentrioxyd ved fremstillingen av katalysatoren er av avgjørende betydning. Det sentrale trekk utgjøres av den kjensgjerning at katalysatorens stabilitet, aktivitet og selektivitet forbedres betydelig når i det minste en del av det for fremstilling av katalysatoren-anvendte molybden tilføres i form av molybdentrioxyd. The most important feature of the present invention is the preparation of the catalyst used. The introduction of molybdenum trioxide in the manufacture of the catalyst is of decisive importance. The central feature is the fact that the catalyst's stability, activity and selectivity are significantly improved when at least part of the molybdenum used for the production of the catalyst is supplied in the form of molybdenum trioxide.
Ved den foretrukne utførelsesform ifølge oppfinnelsen må molybdentrioxyd tilføres i en slik mengde at det utgjør minst 25% In the preferred embodiment according to the invention, molybdenum trioxide must be added in such a quantity that it amounts to at least 25%
av det molybden som anvendes ved fremstillingen av katalysatorene. For de mer foretrukne katalysatorer ifølge oppfinnelsen tilføres minst 50% av det ved fremstillingen av katalysatorene anvendte molybden i form av molybdentrioxyd. of the molybdenum used in the production of the catalysts. For the more preferred catalysts according to the invention, at least 50% of the molybdenum used in the manufacture of the catalysts is supplied in the form of molybdenum trioxide.
De katalysatorer som imidlertid er av den største interesse for utførelse av den foreliggende fremgangsmåte under erholdelse av optimale resultater, er blitt fremstilt ved at hele mengden av det anvendte molybden tilføres i form av molybdentrioxyd. The catalysts which, however, are of the greatest interest for carrying out the present method while obtaining optimal results, have been prepared by supplying the entire quantity of the molybdenum used in the form of molybdenum trioxide.
Ved fremstillingen av katalysatorene ifølge oppfinnelsenIn the production of the catalysts according to the invention
kan de metoder som anvendes for innføring av molybdentrioxyd, variere sterkt. En rekke forskjellige metoder er kjente for fagmannen. Innføringen av molybdentrioxyd ved fremstillingen av katalysatorene kan gjøres før eller efter tilsetningen av de øvrige katalysatorkomponenter. the methods used for introducing molybdenum trioxide can vary greatly. A number of different methods are known to those skilled in the art. The introduction of molybdenum trioxide during the production of the catalysts can be done before or after the addition of the other catalyst components.
Ved den mest foretrukne utførelsesform ifølge oppfinnelsen fremstilles katalysatorene i en tilbakeløpsdestillert vandig oppslemning av molybdentrioxyd. In the most preferred embodiment according to the invention, the catalysts are prepared in a reflux-distilled aqueous slurry of molybdenum trioxide.
Som nevnt kan de katalysatorer som anvendes for utførelse av den foreliggende fremgangsmåte, være en hvilken som helst katalysator som er representert ved den ovenstående formel. Katalysatorene kan fremstilles ved hjelp av en rekke forskjellige metoder som er kjente for fagmannen, som samutfelling av opp-løselige salter, inndampning for tørring eller blanding av oxyder, fulgt av kalsinering av de erholdte katalysatorer. Don s-pesielle As mentioned, the catalysts used for carrying out the present method can be any catalyst represented by the above formula. The catalysts can be prepared using a number of different methods known to those skilled in the art, such as co-precipitation of soluble salts, evaporation for drying or mixing of oxides, followed by calcination of the obtained catalysts. Don s-special
metode som anvendes for fremstilling av katalysatorene, er ikke av avgjørende betydning. method used for the production of the catalysts is not of decisive importance.
Ved den foretrukne metode for fremstilling av katalysatorene som anvendes for utførelse av den foreliggende fremgangsmåte, til-bakeløpsdestilleres en vandig.oppslemning av molybdentrioxyd i 1,5-3 timer, hvorefter forbindelser som inneholder fosfor og de øvrige katalysatorkomponenter tilsettes, den vandige blanding kokes til In the preferred method for producing the catalysts used for carrying out the present method, an aqueous slurry of molybdenum trioxide is refluxed for 1.5-3 hours, after which compounds containing phosphorus and the other catalyst components are added, the aqueous mixture is boiled until
o en pasta som tørkes i luft ved 110-120 C, og de erholdte katalysatorer knuses og siktes for å undersøkes. Det foretrekkes å anvende opp-løselige salter av de andre katalysatorkomponenter enn molybden, o a paste that is dried in air at 110-120 C, and the catalysts obtained are crushed and sieved to be examined. It is preferred to use soluble salts of the catalyst components other than molybdenum,
men uoppløselige salter eller oxyder kan også anvendes. Egnede fosforforbindelser som kan anvendes ved fremstillingen av katalysatorene, omfatter orthofosforsyre, metafosforsyre, trifosforsyre, fosforpentabromid og fosforpentaklorid eller lignende forbindelser. De øvrige katalysatorkomponenter kan tilsettes som oxyd, acetat, formiat, sulfat, nitrat eller carbonat eller lignende forbindelser. but insoluble salts or oxides can also be used. Suitable phosphorus compounds which can be used in the production of the catalysts include orthophosphoric acid, metaphosphoric acid, triphosphoric acid, phosphorus pentabromide and phosphorus pentachloride or similar compounds. The other catalyst components can be added as oxide, acetate, formate, sulphate, nitrate or carbonate or similar compounds.
Foretrukne katalysatorer for utførelse av den foreliggende fremgangsmåte fremstilles ved å tilsette forbindelser som inneholder fosfor, krom og minst en forbindelse som inneholder et element A, til en tilbakeløpsdestillert vandig oppslemning av molybdentrioxyd. Mer foretrukne katalysatorer for utførelse av den foreliggende fremgangsmåte fremstilles ved å tilsette forbindelser som inneholder fosfor, og minst én forbindelse som inneholder et element A, til en tilbakeløpsdestillert vandig oppslemning av molybdentrioxyd. De mest foretrukne katalysatorer for utførelse av den foreliggende fremgangsmåte fremstilles imidlertid ved tilsetning av forbindelser av fosfor og minst ettelement bestående av rubidium, cesium eller tallium. Preferred catalysts for carrying out the present process are prepared by adding compounds containing phosphorus, chromium and at least one compound containing an element A to a reflux distilled aqueous slurry of molybdenum trioxide. More preferred catalysts for carrying out the present process are prepared by adding compounds containing phosphorus, and at least one compound containing an element A, to a reflux distilled aqueous slurry of molybdenum trioxide. However, the most preferred catalysts for carrying out the present method are prepared by adding compounds of phosphorus and at least one element consisting of rubidium, cesium or thallium.
Reaktantene ved fremgangsmåten ifølge op<p>finnelsen er acrolein eller methacrolein og molekylært oxygen. Molekylært oxygen tilføres vanligvis til reaksjonen i form av luft, men oxygen-gass kan også anvendes. 0,5-10 mol oxygen tilsettes vanligvis pr. mol acrolein eller methacrolein. The reactants in the method according to the invention are acrolein or methacrolein and molecular oxygen. Molecular oxygen is usually supplied to the reaction in the form of air, but oxygen gas can also be used. 0.5-10 mol of oxygen is usually added per moles of acrolein or methacrolein.
Vanndamp eller et inert fortynningsmiddel kan eventuelt tilsettes til reaktantene. De foretrukne omsetninger utføres i nærvær av vesentlige mengder vanndamp av 2-20 mol vanndamp pr. mol acrolein eller methacrolein. Water vapor or an inert diluent can optionally be added to the reactants. The preferred reactions are carried out in the presence of significant amounts of water vapor of 2-20 mol water vapor per moles of acrolein or methacrolein.
Reaksjonstemperaturen kan variere med de forskjellige an- The reaction temperature can vary with the different an-
vendte katalysatorer. Temperaturer på 200-500°C anvendes som regel, og temperaturer på 250-400°C er foretrukne. reversed catalysts. Temperatures of 200-500°C are used as a rule, and temperatures of 250-400°C are preferred.
Reaksjonen kan bekvemt utføres i en reaktor med statiskThe reaction can conveniently be carried out in a reactor with static
lag eller med hvirvelskikt. Kontakttiden kan være så lav som brøk-delen av et sekund eller så høy som 20 sekunder eller derover, og den foretrukne kontakttid er 4-5 sekunder. Omsetningen kan utføres ved atmosfæretrykk, overatmosfærisk trykk eller underatmosfærisk trykk, idet det foretrekkes å anvende et absolutt trykk på 0,5- layers or with swirl layers. The contact time can be as low as a fraction of a second or as high as 20 seconds or more, and the preferred contact time is 4-5 seconds. The reaction can be carried out at atmospheric pressure, superatmospheric pressure or subatmospheric pressure, it being preferable to use an absolute pressure of 0.5-
4 atmosfærer.4 atmospheres.
Katalysatoren kan anvendes i reaktoren i båret eller ubåret form. Egnede bærermaterialer omfatter siliciumdioxyd, aluminium-oxyd, bor, fosfat, zirkoniumdioxyd eller titan etc. men det mest foretrukne bærermateriale. er zirkoniumdioxyd. The catalyst can be used in the reactor in supported or unsupported form. Suitable carrier materials include silicon dioxide, aluminum oxide, boron, phosphate, zirconium dioxide or titanium etc. but the most preferred carrier material. is zirconium dioxide.
De nedenstående eksempler er representative for fremstilling av katalysatorer som er egnede for utførelse av den foreliggende fremgangsmåte. Den foretrukne omsetning som utføres ved The following examples are representative of the production of catalysts which are suitable for carrying out the present method. The preferred turnover carried out by
fremgangsmåten ifølge oppfinnelsen, er oxydasjon av methacroleinthe method according to the invention is oxidation of methacrolein
til methacrylsyre. Selvfølgelig kan acrolein omdannes til acrylsyre ved anvendelse av de beskrevne katalysatorer og den foreliggende fremgangsmåte. to methacrylic acid. Of course, acrolein can be converted to acrylic acid using the described catalysts and the present method.
Spesielle utførelsesformerSpecial embodiments
Eksempel 1, sammenligningseksempler A, B og CExample 1, Comparative Examples A, B and C
Fremstilling av methacrylsyre ved anvendelse av en katalysator med formelen Rb qMo_P ,.,.0 , fremstilt fra molybdentrioxyd, sammenlignet med fremstilling av methacrylsyre ved anvendelse av den samme katalysator, men fremstilt fra forskjellige molybdenutgangsmaterialer. Production of methacrylic acid using a catalyst of the formula Rb qMo_P ,.,.0 , prepared from molybdenum trioxide, compared to production of methacrylic acid using the same catalyst, but prepared from different molybdenum starting materials.
Eksempel 1Example 1
Fremstilling fra molybdentrioxyd.Production from molybdenum trioxide.
En vandig oppslemning ble fremstilt ved tilsetning avAn aqueous slurry was prepared by adding
55,3 g molybdentrioxyd til 1 liter kokende, destillert vann under omrøring. Oppslemningen ble kokt i ca. 2 timer. 4,9 g 85%-ig fosforsyre ble tilsatt til denne vandige oppslemning, og oppslemningens farve ble forandret til gul. For å opprettholde en oppløsning i en mengde av ca. 800 ml ble ca. 200 ml destillert vann tilsatt. Efter ca. 1,5 timer fra tilsetningen av den 85%-igefosfor-syre forandret oppslemningen farve til tydelig gulgrønn. Derefter 55.3 g of molybdenum trioxide to 1 liter of boiling, distilled water while stirring. The slurry was boiled for approx. 2 hours. 4.9 g of 85% phosphoric acid was added to this aqueous slurry, and the slurry's color changed to yellow. To maintain a solution in an amount of approx. 800 ml was approx. 200 ml of distilled water added. After approx. 1.5 hours from the addition of the 85% phosphoric acid, the slurry changed color to a distinct yellow-green. After that
ble 100 ml destillert vann tilsatt for å opprettholde oppløsningens volum. 7,5 g rubidiumcarbonat ble tilsatt til den vandige blanding. 100 ml of distilled water was added to maintain the volume of the solution. 7.5 g of rubidium carbonate was added to the aqueous mixture.
Oppslemningens farve ble lysegul. Efter ca. 30 minutter ble 25 ml destillert vann tilsatt. Katalysatoren ble oppvarmet under omrøring, kokt til tørrhet og tørket i luft ved en temperatur på ca. 110°C. The color of the slurry became light yellow. After approx. After 30 minutes, 25 ml of distilled water was added. The catalyst was heated with stirring, boiled to dryness and dried in air at a temperature of approx. 110°C.
Sammenligningseksempel AComparative example A
Fremstilling fra fosformolybdensyre.Production from phosphormolybdic acid.
En vandig oppløsning ble fremstilt ved å oppløse 118,3 g fosformolybdensyre i ca. 1400 ml destillert vann. Til denne opp-løsning ble 1,92 g 85%-ig fosforsyre tilsatt. Den blekgule opp-løsning ble kokt i ca. 8 timer og omrørt uten oppvarming i 12 An aqueous solution was prepared by dissolving 118.3 g of phosphormolybdic acid in approx. 1400 ml of distilled water. 1.92 g of 85% phosphoric acid was added to this solution. The pale yellow solution was boiled for approx. 8 hours and stirred without heating for 12
timer. Oppvarmingen ble gjenopptatt, 11,6 g rubidiumcarbonat ble tilsatt, og oppløsningen forandret hurtig farve til lysegul. Den vandige blanding ble kokt til tørrhet og tørket over natten i luft ved 110°C. hours. Heating was resumed, 11.6 g of rubidium carbonate was added, and the solution rapidly changed color to pale yellow. The aqueous mixture was boiled to dryness and dried overnight in air at 110°C.
Sammenligningseksempel BComparative example B
Fremstilling fra ammoniumheptamolybdat.Preparation from ammonium heptamolybdate.
En oppslemning bestående av 105,9 g ammoniumheptamolybdat r (NH4)gMo7024. 4H20, 7,7 g 85%-ig fosforsyre dg 1400 ml destillert vann ble kokt under omrøring. Oppslemningen forandret langsomt farve fra blekt gul til hvit. Efter koking ble oppslemningen om- A slurry consisting of 105.9 g of ammonium heptamolybdate r (NH4)gMo7024. 4H 2 O, 7.7 g of 85% phosphoric acid and 1400 ml of distilled water were boiled with stirring. The slurry slowly changed color from pale yellow to white. After boiling, the slurry was re-
rørt uten oppvarming i 12 timer. Oppvarmingen ble gjenopptatt,stirred without heating for 12 hours. The heating was resumed,
og 11,6 g rubidiumcarbonat ble tilsatt. Den vandige blandings farve holdt seg hvit. Den vandige blanding ble kokt til tørrhet og tørket over natten i luft ved 110°C. and 11.6 g of rubidium carbonate was added. The color of the aqueous mixture remained white. The aqueous mixture was boiled to dryness and dried overnight in air at 110°C.
Sammenligningseksempel CComparative example C
Fremstilling fra molybdensyre. Production from molybdic acid.
Denne katalysator ble fremstilt på samme måte som beskrevetThis catalyst was prepared in the same way as described
i sammenligningseksempel B, men med den unntagelse at 7,7 g 85%-ig fosforsyre ble anvendt og at ammoniumheptamolybdat ble erstattet med 101,6 g molybdensyre. in comparative example B, but with the exception that 7.7 g of 85% phosphoric acid was used and that ammonium heptamolybdate was replaced by 101.6 g of molybdic acid.
Katalysatorene fremstilt ifølge eksempel 1 og sammenlignings-i eksemplene A, B og C ble malt og siktet for gjenvinning av partiklene med en størrelse på 20-30 mesh. En porsjon av disse katalysator-partikler ble fylt i en 20 cm 3 reaktor med statisk lag og som besto av 1,3 cm rør av rustfritt stål forsynt med en 0,3 cm aksial termo-brønn. Reaktoren ble oppvarmet til en reaksjonstemperatur av 343°C The catalysts prepared according to example 1 and comparative examples A, B and C were ground and sieved to recover the particles with a size of 20-30 mesh. A portion of these catalyst particles was filled into a 20 cm 3 static bed reactor consisting of 1.3 cm stainless steel tubing fitted with a 0.3 cm axial thermo-well. The reactor was heated to a reaction temperature of 343°C
under en luftstrøm, og en tilførselsblanding av methacrolein/luft/ vanndamp i et forhold av 1:6,2:5,2 ble ført over katalysatoren i en tilsynelatende kontakttid på 4,6 sekunder. under an air stream, and a feed mixture of methacrolein/air/water vapor in a ratio of 1:6.2:5.2 was passed over the catalyst for an apparent contact time of 4.6 seconds.
I sammenligningseksemplene B og C ble katalysatorene, kalsinert i 1 time ved 430°C, hvorefter temperaturen ble senket til 343°C. Reaktoren ble drevet under reaksjonsbetingelsene i 1,6 timer, og produktet ble derefter oppsamlet ved at avgassene fra reaktoren ble vasket i to grupper av vannvaskeapparater. Inn-holdene fra vaskeapparatene ble kombinert og fortynnet til 100 cm<3>for analyse og titrering for å fastslå syreinnholdet. De vaskede bundne gasser ble tørket og analysert ved hjelp av et vanlig spalte-kolonnesystem av typen Ho.udry. Resultatene av disse forsøk er gjengitt i den nedenstående tabell I. De følgende definisjoner anvendes under måling av carbonatomene i tilførselsmaterialet og produktene. In comparative examples B and C, the catalysts were calcined for 1 hour at 430°C, after which the temperature was lowered to 343°C. The reactor was operated under the reaction conditions for 1.6 hours, and the product was then collected by washing the off-gases from the reactor in two groups of water scrubbers. The contents of the washers were combined and diluted to 100 cm<3> for analysis and titration to determine the acid content. The washed bound gases were dried and analyzed by means of a conventional column column system of the Ho.udry type. The results of these tests are reproduced in Table I below. The following definitions are used when measuring the carbon atoms in the feed material and the products.
Eksempler 2- 5 Examples 2-5
Innvirkning av driftstiden på katalysatoraktiviteten ved anvendelse av katalysatoren Rb „ rMo,P. ,.0 . Influence of the operating time on the catalyst activity when using the catalyst Rb „ rMo,P. ,.0 .
0, 5 30,33x 0.5 30.33x
Katalysatoren fremstilt som beskrevet i eksempel 1 og omsatt med methacrolein, ble holdt i bruk for ytterligere bestem-melse av methacroleinomdannelsen til methacrylsyre. Resultatene av dette forsøk er gjengitt i tabell II. The catalyst prepared as described in Example 1 and reacted with methacrolein was kept in use for further determination of the methacrolein conversion to methacrylic acid. The results of this experiment are reproduced in Table II.
E ksempler 6- 10 Examples 6-10
Fremstilling og anvendelse av forskjellige katalysatorer for utførelse av den foreliggende fremgangsmåte. Preparation and use of different catalysts for carrying out the present method.
Forskjellige katalysatorer ifølge oppfinnelsen ble fremstilt. Disse katalysatorer hadde den generelle formel A^ 5Mo3Po 33^x' Katalysatorene ble fremstilt ved fremgangsmåten beskrevet i eksempel 1, men med den unntagelse at 86,2 g MoO^ og 7,7 g 85%-ig H^PO^ble anvendt. Elementet A ble tilsatt efter at fosforsyren var blitt tilsatt. For fremstilling av katalysatorene ble de følgende forbindelser og.mengder anvendt: Various catalysts according to the invention were prepared. These catalysts had the general formula A^ 5Mo3Po 33^x' The catalysts were prepared by the method described in example 1, but with the exception that 86.2 g of MoO^ and 7.7 g of 85% H^PO^ were used. The element A was added after the phosphoric acid had been added. For the production of the catalysts, the following compounds and quantities were used:
Efter at elementet A var blitt tilsatt, /ble katalysatorene kokt og tørket som beskrevet i eksempel 1. Katalysatorene ble malt, siktet og undersøkt som beskrevet i de ovenstående eksempler. Resultatene erholdt ved anvendelse av disse katalysatorer for oxydasjon av methacrolein, er gjengitt i tabell III. After element A had been added, the catalysts were boiled and dried as described in Example 1. The catalysts were ground, sieved and examined as described in the above examples. The results obtained by using these catalysts for the oxidation of methacrolein are reproduced in Table III.
i in
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60536375A | 1975-08-18 | 1975-08-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO762836L true NO762836L (en) | 1977-02-21 |
Family
ID=24423358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO762836A NO762836L (en) | 1975-08-18 | 1976-08-17 |
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| JP (1) | JPS5225712A (en) |
| AT (1) | AT359982B (en) |
| BE (1) | BE845250A (en) |
| CA (1) | CA1059532A (en) |
| CH (1) | CH619919A5 (en) |
| CS (1) | CS196317B2 (en) |
| DD (1) | DD127323A5 (en) |
| DE (1) | DE2634791A1 (en) |
| ES (1) | ES450762A1 (en) |
| FR (1) | FR2321474A1 (en) |
| GB (1) | GB1526365A (en) |
| IN (1) | IN145503B (en) |
| IT (1) | IT1065801B (en) |
| NL (1) | NL7609182A (en) |
| NO (1) | NO762836L (en) |
| PT (1) | PT65454B (en) |
| RO (1) | RO69968A (en) |
| YU (1) | YU195176A (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1320461A (en) * | 1962-04-19 | 1963-03-08 | Shell Int Research | Process for preparing unsaturated monocarboxylic acids from olefins |
| US3686294A (en) * | 1970-10-06 | 1972-08-22 | Japanese Geon Co Ltd | Process for the production of methacrylic acid |
| BE789241A (en) * | 1971-09-28 | 1973-03-26 | Halcon International Inc | Catalyst for the oxidation of unsaturated aldehydes |
| DE2251364B2 (en) * | 1971-10-22 | 1975-07-03 | Asahi Glass Co. Ltd., Tokio | Process for the production of acrylic acid or methacrylic acid from acrolein or methacrolein |
| IT971370B (en) * | 1972-11-30 | 1974-04-30 | Sir Soc Italiana Resine Spa | PERFECTED PROCESS FOR THE PRODUCTION OF ACROLEIN AND ACRYLIC ACID |
| JPS5413876B2 (en) * | 1974-10-23 | 1979-06-02 |
-
1976
- 1976-07-20 IN IN1301/CAL/76A patent/IN145503B/en unknown
- 1976-07-29 CA CA258,069A patent/CA1059532A/en not_active Expired
- 1976-08-03 DE DE19762634791 patent/DE2634791A1/en not_active Withdrawn
- 1976-08-05 RO RO7687217A patent/RO69968A/en unknown
- 1976-08-05 AT AT582976A patent/AT359982B/en not_active IP Right Cessation
- 1976-08-06 IT IT26137/76A patent/IT1065801B/en active
- 1976-08-09 PT PT65454A patent/PT65454B/en unknown
- 1976-08-10 JP JP51096587A patent/JPS5225712A/en active Pending
- 1976-08-10 YU YU01951/76A patent/YU195176A/en unknown
- 1976-08-16 CH CH1043276A patent/CH619919A5/de not_active IP Right Cessation
- 1976-08-16 DD DD194342A patent/DD127323A5/xx unknown
- 1976-08-16 CS CS765326A patent/CS196317B2/en unknown
- 1976-08-16 FR FR7624877A patent/FR2321474A1/en active Pending
- 1976-08-17 BE BE169860A patent/BE845250A/en not_active IP Right Cessation
- 1976-08-17 NO NO762836A patent/NO762836L/no unknown
- 1976-08-17 ES ES450762A patent/ES450762A1/en not_active Expired
- 1976-08-18 NL NL7609182A patent/NL7609182A/en not_active Application Discontinuation
- 1976-08-18 GB GB34384/76A patent/GB1526365A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| RO69968A (en) | 1981-06-26 |
| FR2321474A1 (en) | 1977-03-18 |
| ES450762A1 (en) | 1977-08-01 |
| CS196317B2 (en) | 1980-03-31 |
| IT1065801B (en) | 1985-03-04 |
| PT65454B (en) | 1978-02-10 |
| DD127323A5 (en) | 1977-09-21 |
| PT65454A (en) | 1976-09-01 |
| ATA582976A (en) | 1980-05-15 |
| CA1059532A (en) | 1979-07-31 |
| AT359982B (en) | 1980-12-10 |
| IN145503B (en) | 1978-10-28 |
| GB1526365A (en) | 1978-09-27 |
| CH619919A5 (en) | 1980-10-31 |
| NL7609182A (en) | 1977-02-22 |
| YU195176A (en) | 1982-05-31 |
| JPS5225712A (en) | 1977-02-25 |
| DE2634791A1 (en) | 1977-03-03 |
| BE845250A (en) | 1976-12-16 |
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