CA1057764A - Supported catalyst for the oxidation of o-xylene or naphthalene to phthalic anhydride - Google Patents
Supported catalyst for the oxidation of o-xylene or naphthalene to phthalic anhydrideInfo
- Publication number
- CA1057764A CA1057764A CA224A CA224A CA1057764A CA 1057764 A CA1057764 A CA 1057764A CA 224 A CA224 A CA 224A CA 224 A CA224 A CA 224A CA 1057764 A CA1057764 A CA 1057764A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- supported catalyst
- anatase
- active material
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 12
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims abstract description 10
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229940078552 o-xylene Drugs 0.000 title claims abstract description 10
- 230000003647 oxidation Effects 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011149 active material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229940022663 acetate Drugs 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000286904 Leptothecata Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- -1 aluminas Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229940044170 formate Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Furan Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the catalytic oxidation of o-xylene or naphthalene with air to form phthalic anhydride wherein a supported catalyst is used comprising an inert nonporous carrier and applied thereto a thin layer of catalytically active material which comprises from 1 to 40% by weight of vanadium pentoxide and from 60 to 99% by weight of anatase and which has a vanadium pentoxide content of from 0.05 to 4% by weight based on the supported catalyst wherein the catalytically active material contains from 0.01 to 0.15% by weight of rubidium or caesium in the form of a compound devoid of sulfur, based on anatase.
A process for the catalytic oxidation of o-xylene or naphthalene with air to form phthalic anhydride wherein a supported catalyst is used comprising an inert nonporous carrier and applied thereto a thin layer of catalytically active material which comprises from 1 to 40% by weight of vanadium pentoxide and from 60 to 99% by weight of anatase and which has a vanadium pentoxide content of from 0.05 to 4% by weight based on the supported catalyst wherein the catalytically active material contains from 0.01 to 0.15% by weight of rubidium or caesium in the form of a compound devoid of sulfur, based on anatase.
Description
~0577~4 This invention relates to a process for the catalytic oxidation of o-xylene or naphthalene wlth air to form phthalic anhydride.
Canadi`an patents Nos. 846,837 and 862,735 disclose supported catalysts which consist of a nonporous carrier material and an active material applied thereto in a thin layer and containing essentially vanadium pentoxide and titanium dioxide. These catalysts which are suitable for the production of phthalic anhydride by air oxidation of o-xylene or naphthalene have contents, based on the active material, of for example from 1 to 30% by weight of vanadium pentoxide, from 99 to 70%
by weight of titanium dioxide and, based on the supported catalyst, from 0.05 to 3% by weight of vanadium pentoxide.
It has been found that surprisingly these catalysts when they are devoid of alkali metal compounds in the catalytically active material display a very high activity in the catalytic oxidation of o-xylene in a tube reactor at only fairly low bath temperatures. The strong activity is evidenced by the fact ' that there develops in the catalyst filling of the tube a hot spot having a very narrow extent and a temperature of more than 500 C. There is therefore the risk that there may be partial decomposition of the hydrocarbon to maleic acid and to oxides of the hydrocarbon resulting in a decrease in the yield and quality of the phthalic anhydride. Since this hot spot is too high the bath temperature has to be decreased and a drop in temperature of only 20C may cause cessation of the reaction.
When alkali metal compounds are added to these catalysts or use is made in their production of a commercially available type of anatase (which contains 0.2% by weight or more of an alkali metal in the form of the oxide to avoid conversion into rutile) the oxidation of crude hydrocarbons, which always contain sulfur, results in the ~ormation of alkali metal sulfates or purosulfates which not only retard the catalytic effect but also form melts with the vanadium pentoxide so that some of the vanadium pentoxide is removed from the catalyst.
Moreover inactivation of the vanadium pentoxide takes place.
We have now found a process for the catalytic oxidation of o-xylene or naphthalene with air to form phthalic anhydride wherein a supported catalyst is used comprising an inert nonporous carrier and applied thereto a thin layer of catalytically active material which comprises from 1 to 40% by weight of vanadium pentoxide and from 60 to 99% by weight of anatase and which has a vanadium pentoxide content of from 0.05 to 4% by weight based on the supported catalyst wherein the catalytically active material contains from 0.01 to 0.15% by weight of rubidium or caesium in the form of a compound devoid of sulfur, based on anatase.
The catalysts advantageously contain sintered or fused silicates, porcelain, aluminas, silicon carbide, rutile , or quartz as the inert nonporous material. The carrier advantageously has the shape of a sphere having a diameter of from 4 to 12 mm.
The catalytic material applied to the carrier advantageously has a layer thickness of for example from 0.04 to 0.2 mm. The active material advantageously forms from about 3 to 10% by weight of the supported catalyst.
The anatase advantageously has an internal surface area of from 8 to 15 m2 per gram and a particle size of less than 1 micron, for example from 0.4 to 0.8 micron. The catalytically active material contains from 0.01 to 0.15%
3Q and preferably from 0.01 to 0.1% by weight of rubidium or caesium, based on the anatase.
/~
10577~4 The said alkali metals are added to the catalytical-ly active material in the form of compolmds devoid of ~ulfur, for example in the form of their oxides or other oxygen-containing compounds such as carbonates or acetate~ in the production of the catalysts.
In addition to the said constituent3 the active ma-terial may contain from 0.1 to 3~ by weight and particularly from 0.2 to 1% by weight of phosphorus in the form of a com-pound and preferably in the form of pho~phoric acid or a ni-trogenous compound thereof such as an ammonium salt and/orfrom 0.1 to 15~ by weight of a compound and conveniently an oxide of the element~ aluminum, zirconium, antimony, arsenic, niobium, chromium, molybdenum, tungsten, cobalt or nickel.
The catalysts may be prepared by conventional me-thods, for example by mixing a vanadium compound which is con-verted into vanadium pentoxide when heated such as ammonium vanadate or the oxalate, formate, acetate, tartrate or sali-cylate of vanadium in water or an organic solvent such as formamide, diethylacetamide, ammonium thiocyanate, fu~ed urea or an alcohol ~ith finely divided anatase with the addition fo rubidiwn carbonate solution or caesium carbonate ~olution with or without ammonium dihydrogen pho~phat~ and spraying the mixture, which usually has a pasty consistency, onto the carrier which has been preheated to ]50 to 450C, ~or example in a coating drum. The finely divided ana-ta~e may be obtained for e~ample by grinding, advantageously in a colloid mill When used for the production of phthalic anhydride the new supported catalysts are placed in conventional manner for example in a tubular reactor whose tube3 have a diameter of from 25 to 40 mm and contacted with the mixture of hydro-carbon and air.
The dlameter of the 3phere~ of carrier i~ convenien-_~_ lOS'~7f~
tly cho3en so that it is about one third o the diameter of the tubes. When a tube hav~ng an internsl width of 25 mm is used, s~heres havlng a diameter of from 7.5 to 8.2 mm are ad-vantageou~ly used. The same spheres or tho~e having a diame-ter which is about one third of the diameter of the tubes may be used in the ca~se of tubes of larger diameter.
In carrying out the oxidàtion the ttlbes are surroun-ded by a salt bath melt having a temperature of from about 360 to 425C to control the temperature. The hydrocarbon is passed together with air which has previously been advanta-geously heated to 150 to 300C through the tube~, the maximum temperature (hot spot) occurring in the fir~t thrid of the layer of catalyst and not being allowed to e~ceed 500C for a long time. The hourly loading of the catalyst i~ generally from about ~000 to 10,000 liter~ of air with about 40 g of hydrocarbon for each 1000 liters of air. The maximum internal temperature (hot spot) is controlled with the salt bath tem-peratvre.
The following Examples illu~trate the invention.
EXAMPI.E I
1,800 g of steatite ~pheres of 6 mm diameter are heated to 300C in a coating drum. The hot spheres are sprayed, ~hilst maintaining the above temperature, with a suspension consi~ting of 400 g of finely ground alkali-free anatase ha-ving an internal surface area of 11 m2/g, 42.2 g of vanadyl oxalate in 400 ml of water, 140 ml of formamide, 200 ml of ~,rater and 0.58 g of rubidium carbonate 1mtil they have taken up 6~ o~ catalytic material.
The catalytic material contains 93.89~ by weight of a~ata~e, 6% by weight of vanadium pentoxide and 0.11~ by weight of Rb20, correspon~ing to 0.10% by wei~ht of rubidium.
The cata]"yst i9 introduced into a tube of 25 mm lOS77~4 internal diameter and 3 m length, surrounded by a salt bath 5,000 liters (S.T.P,) of air per hour are pa3sed through the catalyst bed. Using a salt bath temperature of 375C and charging the air with 40 g of o-xylene per cubic meter (S.T.P.), the yield i9 109~ by weight of phthalic anhydride, based on 100~ pure o-xylene, after 40 days' operation, 110% by weight after 55 dsys and lll~o by weight after 80 days.
1,800 g of steatite spheres of 6 mm diameter are heated to 300C in a coating drum. The hot spheres are sprayed, whilst maintaining the above temperature, with a suspension consisting of 400 g of finely ground alkali-free anatase having an internal surface area of 11 m2/g, 42.2 g of vanadyl oxalate in 400 ml of water, 140 ml of formamide, 200 ml of water and 0.40 g of caesium carbonate until they have taken up 6 . O~o of catalytic material.
The catalytic material contains 93. 92~o by weight of anatase, 6.0~o by weight of vanadium pentoxide and 0,08% by weight of Cs20, corre3ponding to 0.076% by weight of caesium The catalyst is introduced into a tube of 25 mm internal diameter and 3 m length, surrounded by a salt bath.
5,000 liter~ (S.T.P,) of air per hour are passed through the catalyst bed. At a salt bath temperature of 380C and char-ging the air with from 40 to 42 g of 0-xylene/cubic meter, a yield of 109.5~o by weight of phthalic anhydride, based on lOO~o pure o-xylene, is obtained.
Canadi`an patents Nos. 846,837 and 862,735 disclose supported catalysts which consist of a nonporous carrier material and an active material applied thereto in a thin layer and containing essentially vanadium pentoxide and titanium dioxide. These catalysts which are suitable for the production of phthalic anhydride by air oxidation of o-xylene or naphthalene have contents, based on the active material, of for example from 1 to 30% by weight of vanadium pentoxide, from 99 to 70%
by weight of titanium dioxide and, based on the supported catalyst, from 0.05 to 3% by weight of vanadium pentoxide.
It has been found that surprisingly these catalysts when they are devoid of alkali metal compounds in the catalytically active material display a very high activity in the catalytic oxidation of o-xylene in a tube reactor at only fairly low bath temperatures. The strong activity is evidenced by the fact ' that there develops in the catalyst filling of the tube a hot spot having a very narrow extent and a temperature of more than 500 C. There is therefore the risk that there may be partial decomposition of the hydrocarbon to maleic acid and to oxides of the hydrocarbon resulting in a decrease in the yield and quality of the phthalic anhydride. Since this hot spot is too high the bath temperature has to be decreased and a drop in temperature of only 20C may cause cessation of the reaction.
When alkali metal compounds are added to these catalysts or use is made in their production of a commercially available type of anatase (which contains 0.2% by weight or more of an alkali metal in the form of the oxide to avoid conversion into rutile) the oxidation of crude hydrocarbons, which always contain sulfur, results in the ~ormation of alkali metal sulfates or purosulfates which not only retard the catalytic effect but also form melts with the vanadium pentoxide so that some of the vanadium pentoxide is removed from the catalyst.
Moreover inactivation of the vanadium pentoxide takes place.
We have now found a process for the catalytic oxidation of o-xylene or naphthalene with air to form phthalic anhydride wherein a supported catalyst is used comprising an inert nonporous carrier and applied thereto a thin layer of catalytically active material which comprises from 1 to 40% by weight of vanadium pentoxide and from 60 to 99% by weight of anatase and which has a vanadium pentoxide content of from 0.05 to 4% by weight based on the supported catalyst wherein the catalytically active material contains from 0.01 to 0.15% by weight of rubidium or caesium in the form of a compound devoid of sulfur, based on anatase.
The catalysts advantageously contain sintered or fused silicates, porcelain, aluminas, silicon carbide, rutile , or quartz as the inert nonporous material. The carrier advantageously has the shape of a sphere having a diameter of from 4 to 12 mm.
The catalytic material applied to the carrier advantageously has a layer thickness of for example from 0.04 to 0.2 mm. The active material advantageously forms from about 3 to 10% by weight of the supported catalyst.
The anatase advantageously has an internal surface area of from 8 to 15 m2 per gram and a particle size of less than 1 micron, for example from 0.4 to 0.8 micron. The catalytically active material contains from 0.01 to 0.15%
3Q and preferably from 0.01 to 0.1% by weight of rubidium or caesium, based on the anatase.
/~
10577~4 The said alkali metals are added to the catalytical-ly active material in the form of compolmds devoid of ~ulfur, for example in the form of their oxides or other oxygen-containing compounds such as carbonates or acetate~ in the production of the catalysts.
In addition to the said constituent3 the active ma-terial may contain from 0.1 to 3~ by weight and particularly from 0.2 to 1% by weight of phosphorus in the form of a com-pound and preferably in the form of pho~phoric acid or a ni-trogenous compound thereof such as an ammonium salt and/orfrom 0.1 to 15~ by weight of a compound and conveniently an oxide of the element~ aluminum, zirconium, antimony, arsenic, niobium, chromium, molybdenum, tungsten, cobalt or nickel.
The catalysts may be prepared by conventional me-thods, for example by mixing a vanadium compound which is con-verted into vanadium pentoxide when heated such as ammonium vanadate or the oxalate, formate, acetate, tartrate or sali-cylate of vanadium in water or an organic solvent such as formamide, diethylacetamide, ammonium thiocyanate, fu~ed urea or an alcohol ~ith finely divided anatase with the addition fo rubidiwn carbonate solution or caesium carbonate ~olution with or without ammonium dihydrogen pho~phat~ and spraying the mixture, which usually has a pasty consistency, onto the carrier which has been preheated to ]50 to 450C, ~or example in a coating drum. The finely divided ana-ta~e may be obtained for e~ample by grinding, advantageously in a colloid mill When used for the production of phthalic anhydride the new supported catalysts are placed in conventional manner for example in a tubular reactor whose tube3 have a diameter of from 25 to 40 mm and contacted with the mixture of hydro-carbon and air.
The dlameter of the 3phere~ of carrier i~ convenien-_~_ lOS'~7f~
tly cho3en so that it is about one third o the diameter of the tubes. When a tube hav~ng an internsl width of 25 mm is used, s~heres havlng a diameter of from 7.5 to 8.2 mm are ad-vantageou~ly used. The same spheres or tho~e having a diame-ter which is about one third of the diameter of the tubes may be used in the ca~se of tubes of larger diameter.
In carrying out the oxidàtion the ttlbes are surroun-ded by a salt bath melt having a temperature of from about 360 to 425C to control the temperature. The hydrocarbon is passed together with air which has previously been advanta-geously heated to 150 to 300C through the tube~, the maximum temperature (hot spot) occurring in the fir~t thrid of the layer of catalyst and not being allowed to e~ceed 500C for a long time. The hourly loading of the catalyst i~ generally from about ~000 to 10,000 liter~ of air with about 40 g of hydrocarbon for each 1000 liters of air. The maximum internal temperature (hot spot) is controlled with the salt bath tem-peratvre.
The following Examples illu~trate the invention.
EXAMPI.E I
1,800 g of steatite ~pheres of 6 mm diameter are heated to 300C in a coating drum. The hot spheres are sprayed, ~hilst maintaining the above temperature, with a suspension consi~ting of 400 g of finely ground alkali-free anatase ha-ving an internal surface area of 11 m2/g, 42.2 g of vanadyl oxalate in 400 ml of water, 140 ml of formamide, 200 ml of ~,rater and 0.58 g of rubidium carbonate 1mtil they have taken up 6~ o~ catalytic material.
The catalytic material contains 93.89~ by weight of a~ata~e, 6% by weight of vanadium pentoxide and 0.11~ by weight of Rb20, correspon~ing to 0.10% by wei~ht of rubidium.
The cata]"yst i9 introduced into a tube of 25 mm lOS77~4 internal diameter and 3 m length, surrounded by a salt bath 5,000 liters (S.T.P,) of air per hour are pa3sed through the catalyst bed. Using a salt bath temperature of 375C and charging the air with 40 g of o-xylene per cubic meter (S.T.P.), the yield i9 109~ by weight of phthalic anhydride, based on 100~ pure o-xylene, after 40 days' operation, 110% by weight after 55 dsys and lll~o by weight after 80 days.
1,800 g of steatite spheres of 6 mm diameter are heated to 300C in a coating drum. The hot spheres are sprayed, whilst maintaining the above temperature, with a suspension consisting of 400 g of finely ground alkali-free anatase having an internal surface area of 11 m2/g, 42.2 g of vanadyl oxalate in 400 ml of water, 140 ml of formamide, 200 ml of water and 0.40 g of caesium carbonate until they have taken up 6 . O~o of catalytic material.
The catalytic material contains 93. 92~o by weight of anatase, 6.0~o by weight of vanadium pentoxide and 0,08% by weight of Cs20, corre3ponding to 0.076% by weight of caesium The catalyst is introduced into a tube of 25 mm internal diameter and 3 m length, surrounded by a salt bath.
5,000 liter~ (S.T.P,) of air per hour are passed through the catalyst bed. At a salt bath temperature of 380C and char-ging the air with from 40 to 42 g of 0-xylene/cubic meter, a yield of 109.5~o by weight of phthalic anhydride, based on lOO~o pure o-xylene, is obtained.
Claims (9)
1. A process for the catalytic oxidation of o-xylene or naphthalene with air to form phthalic anhydride wherein a supported catalyst is used comprising an inert nonporous carrier and applied thereto a thin layer of catalytically active material which comprises from 1 to 40%
by weight of vanadium pentoxide and from 60 to 99% by weight of anatase and which has a vanadium pentoxide content of from 0.05 to 4% by weight based on the supported catalyst wherein the catalytically active material contains from 0.01 to 0.15% by weight of rubidium or caesium in the form of a compound devoid of sulfur, based on anatase.
by weight of vanadium pentoxide and from 60 to 99% by weight of anatase and which has a vanadium pentoxide content of from 0.05 to 4% by weight based on the supported catalyst wherein the catalytically active material contains from 0.01 to 0.15% by weight of rubidium or caesium in the form of a compound devoid of sulfur, based on anatase.
2. A process as claimed in claim 1 the catalytically active material in the supported catalyst contains from 0.01 to 0.1% by weight of rubidium or caesium, based on anatase.
3. A process as claimed in claim 1 wherein the active material in the supported catalyst constitutes from 3 to 10% by weight of the supported catalyst.
4. A process as claimed in claim 1 wherein the anatase in the supported catalyst has an internal surface area of from 8 to 15 m2 per gram.
5. A process as claimed in claim 1 wherein the carrier of the supported catalyst is in the form of spheres having a diameter of from 4 to 12 mm.
6. A process as claimed in claim 1 wherein the anatase in the supported catalyst has a particle size of less than 1 micron.
7. A process as claimed in claim 1 wherein the anatase in the supported catalyst has a particle size of from 0.4 to 0.8 micron.
8. A process as claimed in claim 1 wherein the active material of the catalyst additionally contains from 0.1 to 3%
by weight of phosphorus in the form of a compound.
by weight of phosphorus in the form of a compound.
9. A process as claimed in claim 1 wherein the active material of the catalyst contains from 0.1 to 15% by weight of an oxide of aluminum, zirconium, antimony, arsenic, niobium, chromium, molybdenum, tungsten, cobalt or nickel.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2421406A DE2421406C2 (en) | 1972-12-12 | 1974-05-03 | Process for the production of phthalic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1057764A true CA1057764A (en) | 1979-07-03 |
Family
ID=5914571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA224A Expired CA1057764A (en) | 1974-05-03 | 1975-04-15 | Supported catalyst for the oxidation of o-xylene or naphthalene to phthalic anhydride |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPS50150688A (en) |
| CA (1) | CA1057764A (en) |
| IT (1) | IT1049403B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7022643B2 (en) | 2002-08-20 | 2006-04-04 | Nippon Shokubai Co., Ltd. | Production process for catalyst |
| JP4295521B2 (en) | 2003-02-13 | 2009-07-15 | 株式会社日本触媒 | Catalyst for producing acrylic acid and method for producing acrylic acid |
| WO2010001732A1 (en) | 2008-06-30 | 2010-01-07 | 株式会社日本触媒 | Method of packing solid particulate substance into fixed-bed multitubular reactor |
| JP2011121048A (en) | 2009-12-09 | 2011-06-23 | Rohm & Haas Co | Method for blending and loading solid catalyst material into tubular structure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2212964C3 (en) * | 1972-03-17 | 1980-01-31 | Basf Ag, 6700 Ludwigshafen | Supported catalyst containing vanadium pentoxide, titanium dioxide and optionally zirconium dioxide, phosphorus and other metal oxides |
-
1975
- 1975-04-08 IT IT22124/75A patent/IT1049403B/en active
- 1975-04-15 CA CA224A patent/CA1057764A/en not_active Expired
- 1975-05-06 JP JP50053285A patent/JPS50150688A/ja active Pending
-
1980
- 1980-12-12 JP JP55174786A patent/JPS5815176B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS50150688A (en) | 1975-12-03 |
| JPS5695337A (en) | 1981-08-01 |
| IT1049403B (en) | 1981-01-20 |
| JPS5815176B2 (en) | 1983-03-24 |
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