CN101939104B - Aromatic hydrocarbon catalytic vapor phase oxidation is become the catalyst of aldehyde, carboxylic acid and/or carboxylic acid anhydrides, particularly phthalic anhydride - Google Patents
Aromatic hydrocarbon catalytic vapor phase oxidation is become the catalyst of aldehyde, carboxylic acid and/or carboxylic acid anhydrides, particularly phthalic anhydride Download PDFInfo
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- CN101939104B CN101939104B CN200980103798.XA CN200980103798A CN101939104B CN 101939104 B CN101939104 B CN 101939104B CN 200980103798 A CN200980103798 A CN 200980103798A CN 101939104 B CN101939104 B CN 101939104B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 619
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 8
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title claims abstract description 7
- 239000012808 vapor phase Substances 0.000 title claims abstract description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title abstract description 31
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 title abstract description 31
- 239000013543 active substance Substances 0.000 claims abstract description 77
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims description 132
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 81
- 239000000126 substance Substances 0.000 claims description 60
- 239000004408 titanium dioxide Substances 0.000 claims description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 abstract description 83
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 83
- 229910052758 niobium Inorganic materials 0.000 abstract description 7
- 239000010955 niobium Substances 0.000 abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 470
- 239000007789 gas Substances 0.000 description 87
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000000203 mixture Substances 0.000 description 27
- 239000012041 precatalyst Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 14
- 230000002349 favourable effect Effects 0.000 description 12
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- 238000000034 method Methods 0.000 description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 8
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- 238000002360 preparation method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
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- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
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- 239000012876 carrier material Substances 0.000 description 5
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- 239000004615 ingredient Substances 0.000 description 5
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- 230000003313 weakening effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
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- ZPUMMRQAZXRERX-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;vanadium Chemical compound [V].OC(=O)C(O)C(O)C(O)=O ZPUMMRQAZXRERX-UHFFFAOYSA-N 0.000 description 1
- TVVDLTQKAVGKLI-UHFFFAOYSA-N 2-hydroxybenzoic acid;vanadium Chemical compound [V].OC(=O)C1=CC=CC=C1O TVVDLTQKAVGKLI-UHFFFAOYSA-N 0.000 description 1
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- 229930194542 Keto Natural products 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical class [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 description 1
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- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 230000037081 physical activity Effects 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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- 150000003482 tantalum compounds Chemical class 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
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- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
-
- 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
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Abstract
The present invention relates to one and aromatic hydrocarbon catalytic vapor phase oxidation is become aldehyde, carboxylic acid and/or carboxylic acid anhydrides, the particularly catalyst of phthalic anhydride, this catalyst has multiple different catalyst layer, wherein, catalyst has hot spot catalyst layer, at least one be placed in this hot spot catalyst layer before catalyst layer and a preferably at least catalyst layer being placed in after this hot spot catalyst layer, the highest local temperature extreme value based on whole catalyst comes across this hot spot catalyst layer. Being present in the catalytic active substance of hot spot catalyst layer according to antimony of the present invention and/or bismuth and/or niobium, in the catalytic active substance of at least one preposition catalyst layer, in these elements, the content of at least one element reduces value set in advance relative to the content of this element in the catalytic active substance of hot spot catalyst layer.
Description
The present invention relates to the catalyst that aromatic hydrocarbon catalytic vapor phase oxidation is become aldehyde, carboxylic acid and/or carboxylic acid anhydrides, particularly phthalic anhydride according to claim 1 preamble.
It is known that industrially in fixed bed reactors, it is preferred in bundled tube reactor, preparing big quantity carboxylic acid and/or carboxylic acid anhydrides by aromatic hydrocarbon catalytic vapor phase oxidation, aromatic hydrocarbon is such as benzene, dimethylbenzene, naphthalene, toluene or durene. This process can such as form benzoic acid, maleic anhydride, phthalic anhydride, M-phthalic acid, p-phthalic acid or 1,2,4,5-pyromellitic anhydride.
For this, generally the mixture being made up of the gas (such as air) of molecule-containing keto and hydrocarbon (such as o-Dimethylbenzene) to be oxidized is guided by so-called bundled tube reactor, a large amount of reaction tubes are arranged in parallel in this bundled tube reactor, and the catalyst windrow being suitable for is present in these reaction tubes. Because will acutely generate heat in these oxidation reactions, so reaction tube must be washed away around by heat transfer medium (such as molten salt bath), thus deriving the heat produced in reaction. Generally use molten salt bath as heat transfer medium, it is preferred to by the mixture of sodium nitrite Yu potassium nitrate.
Although employing this temperature adjusting or temperature stabilization, catalyst windrow still can form local temperature extreme value, i.e. so-called hot spot.
These hot spots will cause a series of effects undesirably occurred, such as raw-material part complete oxidation causes selectivity low, or form more less desirable by-product, such as benzoic acid, maleic anhydride and by o xylene oxidation being 2-benzo (c)-furanone during phthalic anhydride, these by-products of part can must separate through huge consuming, and must lose the end product that part is required. In addition, significantly haveing the disadvantage that of temperature (hot spot) that Part portions in these catalyst beds acutely promotes, in order to realize the peak performance of desired raw material, and when forming one or more hot spot in extreme circumstances, make load be limited to for a long time lower than desired extent, thus avoiding occurring irreversible catalyst to damage, it is necessary to one period of long period of stall after starting running for the first time.
In order to weaken or avoid these hot spots, prior art once used so-called multi-layer catalyst, and it is layer by layer, particularly with stacked catalyst layer, it is arranged in catalyst windrow, wherein, the minimum catalyst of activity is typically closest to gas access, and therefore first it contact with raw mixture.
The high activity excessively of the first catalyst layer will make hot spot temperature that uncontrollable lifting occurs, thus causing the irreversible damage of selectivity reduction mentioned above or catalyst.
In order to ensure the conversion completely of raw material, reducing the content of less desirable by-product as much as possible, from the direction towards gas outlet, the generally activity of catalyst layer rearward is higher simultaneously.
US-A4,356,112 describe one for preparing the catalyst with two different layers of activity of phthalic anhydride, wherein antimony oxide (Sb2O3) content be 0.5 to 10 weight %. Optimum realizes by the catalyst containing 2 weight % stibium oxide and 3 weight % vanadic anhydrides. Disclosed in it, stibium oxide enhances heat stability and the selectivity of catalyst.
EP-A-0522871 describes one for preparing phthalic anhydride by gaseous oxidation and having the catalyst of two different catalyst layers, wherein, employs pentavalent antimony compounds as antimony source. The disclosed catalyst Sb containing 2.5 weight %2O5Or 2.0 Sb of weight %2O3, V2O5��Sb2O3It is 2: 2.0 or V2O5��Sb2O5It is 2: 2.5.
DE10323461A1 describes a kind of method preparing phthalic anhydride, wherein, uses the catalyst with two different layers, and catalyst activity is in rising trend to gas outlet from gas access, and V in ground floor2O5��Sb2O3Ratio be 3.5: 1 to 5: 1.
DE19839001 describes the lamella catalyst of hydrocarbon gas phase oxidation, its Sb2O3Total content is less than 10 weight %, and the catalytic active layer in two or more layers is positioned on inert carrier, and wherein, the antimony oxide total content of inert layer or internal layer is less than 15 weight %, and outermost antimony oxide content reduces by 50% to 100%. Therefore, the active substance of single internal layer or multiple internal layer accounts for the share of gross activity material is 10% to 90%.
EP1084115B1 describes a kind of method of layer oxidation o-Dimethylbenzene superposed by least three and/or naphthalene, and its catalyst activity raises to gas outlet side continuously from side, gas access. Therefore, activity substance content autoreactor entrance to reactor outlet increase, alkali metal content optionally extraly from gas access to gas outlet reduce.
DE10237818 describe a kind of there is the superposed layer of at least three, for manufacturing the catalyst of phthalic anhydride, wherein, layer activity increases continuously to gas outlet from gas access. What this activity increased regulates by using the TiO with different BET surface area2And realize. The BET surface area of the titanium dioxide used is near minimum in the layer of gas access, and the highest being abutted against in the layer of gas outlet most.
EP1063222 describes a method for preparing phthalic anhydride, and wherein, catalyst is made up of three or more different catalyst layers. Reaction carries out in the fixed bed reactors that one or more is superposed. The conversion ratio of used raw material is 30% to 70% after ground floor, and after the second layer is at least 70%.
DE102004026472A1 describes one for preparing the multi-layer catalyst of phthalic anhydride, and its catalyst activity increases on flow direction, and simultaneously the active substance in different layers reduces to gas outlet from gas access.
DE10323817A1 describes a kind of catalyst being prepared phthalic anhydride by least three different layers, wherein, the activity of layer increases to gas outlet from gas access, and only end layer (namely closest to the layer of gas outlet) is phosphorous and containing more than the V of 10 weight %2O5��
WO2006/092304 describes the purposes preparing phthalic anhydride by having the multi-layer catalyst of at least three catalyst layer, and wherein, the activity closest to the ground floor of side, gas access is higher than the activity of the second layer thereafter.
WO2006/092305 describes by a method being prepared phthalic anhydride by least two activity start catalysts that form of different catalyst layers, wherein, closest to gas access ground floor in part through the catalyst replacement with greater activity.
Use the structure as described above catalyst of the variation composition of active material, although the abundant control to local temperature extremal can be realized when raw material load is relatively high, but still exist antigravity system in selectivity aspect, in suppressing to generate by-product aspect, and carry out the needs of bigger improvement in the safety aspect of phthalic anhydride preparation method.
Therefore, it is an object of the invention to, there is provided one that aromatic hydrocarbon catalytic vapor phase oxidation is become aldehyde, carboxylic acid and/or carboxylic acid anhydrides, the particularly catalyst of phthalic anhydride, this catalyst has high selectivity, by-product can be suppressed to generate by this catalyst, and be capable of the high operational safety of the particularly preparation method of phthalic anhydride.
The object of the invention is reached by the feature of claim 1. The theme of dependent claims is preferred embodiment, and their disclosure is incorporated in this specification explicitly by quoting.
As claimed in claim 1, when catalytic active substance at hot spot catalyst layer is antimony and/or bismuth and/or niobium, the content of at least one above-mentioned element of the catalytic active substance of at least one preposition catalyst layer reduces relative to the content of this element of the catalytic active substance of hot spot catalyst layer. Especially preferably, at the antimony content of preposition catalytic active substance at least one catalyst layer of hot spot catalyst layer, especially stibium oxide content, value set in advance is reduced relative to the stibium oxide content of the catalytic active substance in hot spot catalyst layer. According to especially preferred embodiment, antimony content reduces by 20 weight % to 100 weight %, it is most preferred that reduce by 40 weight % to 100 weight %.
Hereinafter the antimony content that contact reduces is described the thinking of the present invention. It is also applied for bismuth or niobium, is specifically described without remaking. This is also suitable in the claims. Although antimony is preferred element among described three described element antimony, bismuth and niobium, but the present invention is merely for the consideration of generality and clearness, has adopted the term " antimony " in the overall invention thinking of claim 1 and " antimony content " in subordinate item. Term " antimony " and " antimony content " therefore both represented " bismuth " and " bi content " on expressing, and represented " niobium " and " content of niobium " again, namely to a certain extent as the upperseat concept of whole three element antimony, bismuth and niobium.
As shown in the experiment of inventor, by preposition this kind at least one catalyst layer of hot spot catalyst layer such as the reduction of the antimony content of the present invention, selectivity can be significantly improved. The formation of by-product can be suppressed simultaneously.
Thinking according to the present invention, hot spot is the maximum local temperature recorded in whole catalyst bed. This maximum hot spot, for 50 to the 120cm depths (from gas access to gas outlet's orientation measurement) being usually located at catalyst bed fresh catalyst, is also possible to occur the secondary hot spot that other is less in other catalyst layer except the hot spot that this is maximum.
Due to hot spot layer along with the working time continue may be located at deep zones or even transfer to the catalyst layer being arranged in depths (to gas outlet direction), so in the present invention preferably in drawing maximum hot spot layer under optimum working temperature (salt temperature), the highest selectivity of catalyst and enough good product quality can be realized in this optimum working temperature, and preferably in after bring into operation the stage (BreakInPeriod) of catalyst, behind be about that catalyst is gone into operation for the first time three months.
Thinking according to the present invention, the concept of catalyst layer with broad understanding, in other words, should not only be interpreted as the coating putting in carrier rings, also include solution, and in such cases, catalyst puts on the carrier that only one runs through. Especially in a broad sense catalyst layer should being interpreted as conversion zone, it is basically identical that the feature of this conversion zone is that catalyst forms in this region, or it is basically identical to be characterized as that when multiple catalysts mixes mixture forms in this region. Therefore, the passage between each catalyst reaction region is unimpeded. It is advantageous to constituted different catalyst by catalyst reaction region, there is between these catalyst more or less unimpeded passage. And different catalyst ordinary meanings is made up of each so-called catalyst ring, catalytic active substance puts in the carrier rings of such as inertia, imporosity in such cases.
For example, the catalytic specie of one or more catalyst layer can point two-layer or more multi-layered put on carrier (especially for ceramic monolith). Preferred way is, flexible program is implemented according to first, the antimony content of the coating that antimony content is the highest relative to antimony content in hot spot catalyst layer, reduces value set in advance by the antimony content of at least one coating of at least one preposition catalyst layer, especially for reducing 20% to 100%. As an alternative or supplement, hot spot catalyst layer has at least two coating for this, wherein, and the coating the highest relative to antimony content, the antimony content of the catalytic active substance of at least one coating in these coatings reduces value set in advance, it is preferable that reduce 20% to 100%. Herein especially can illustratively, relative to internal layer, the antimony content of the catalytic active substance of multiple or at least one layer being arranged on internal layer reduces value set in advance, especially for reducing 20% to 100%. Thus obtaining the advantage in claim 1 also similar to present invention thinking as claimed in claim 1, higher selectivity especially can be realized. The invention flexible program of the multilamellar construction of catalyst layer that what this was mentioned above be related to is not subordinated to the theme of the claims in the present invention 1. In other words, viewpoint according to the present invention, at least one preposition catalyst layer puts in such as carrier rings with multilamellar, but any layer here for described layer, especially be exterior layer, antimony content lower than the antimony content of hot spot catalyst layer (in the hot spot catalyst layer situation of single layer structure); In contrast, when hot spot catalyst layer self has multiple layer and forms heterogeneity, the coating the highest relative to antimony content in hot spot catalyst layer, the antimony content of any layer (most preferably being exterior layer) of preposition catalyst layer is lower.
Embodiment of the present invention according to another especially preferred and same demand for independence protection, it is possible to use the mixture that the catalyst especially different in catalytic active substance forms by least two forms in hot spot catalyst layer. the antimony content of the catalytic active substance of the catalyst the highest relative to antimony content in hot spot catalyst layer, especially it is stibium oxide content, the antimony content of the catalytic active substance of at least one catalyst of hot spot catalyst layer, especially it is stibium oxide content, reduce value set in advance, it is preferable that reduce 20% to 100%. it is also applied for the situation of same demand for independence protection, namely, at the preposition mixture using the catalyst especially different in catalytic active substance forms by least two to form in one or more catalyst layer of this hot spot catalyst layer, wherein, the antimony content of the catalytic active substance of the catalyst the highest relative to antimony content in hot spot catalyst layer, especially it is stibium oxide content, the antimony content of the catalytic active substance of at least one catalyst of the preposition catalyst layer containing catalyst mixture, especially stibium oxide content, reduce value set in advance, preferably reduce 20% to 100%.
Hereafter contact term catalyst layer being described preferred catalyst structure, wherein, when the conversion zone that contact has such as open conduit each other is been described by, this embodiment also belongs to protection domain at technical elements.
According to a preferred embodiment, under only having a preposition catalyst layer situation, the antimony content of the catalytic active substance of this catalyst layer reduces value set in advance relative to the antimony content of the catalytic active substance of hot spot catalyst layer. As an alternative, when there is multiple preposition catalyst layer, in these preposition catalyst layers, the antimony content of at least one of catalytic active substance reduces value set in advance relative to the antimony content of the catalytic active substance of hot spot catalyst layer. High selectivity mentioned above can be obtained by this kind of structure and suppress the generation of less desirable by-product well.
Especially, under the latter event with multiple preposition catalyst layer, the operational stability of phthalic anhydride preparation method also can be significantly increased by this antigravity system.
According to an especially preferred embodiment, in the catalyst layer situation that only one is preposition, the activity substance content of this catalyst layer is less than or equal to the activity substance content of hot spot catalyst layer. As an alternative, when being provided with multiple preposition catalyst layer, these have reduction antimony content precatalyst layer at least one of activity substance content less than or equal to the activity substance content of hot spot catalyst layer.
If the pentoxide content of the catalyst layer that antimony content reduces is 0 weight % to 9 weight %, it is most preferred that is 3 weight % to 6 weight %, then can significantly improve selectivity further.
Additionally, at least one of phosphorus content is 0 weight % to 0.3 weight % in the precatalyst layer of antimony content minimizing, it is most preferred that be 0 weight % to 0.15 weight %, relative to the catalytic active substance of this catalyst layer, then also can improve selectivity of catalyst.
The titles such as the present invention the first catalyst layer used below, the second catalyst layer, the 3rd catalyst layer, the 4th catalyst layer, the 5th catalyst layer will be contacted below: the first catalyst layer is always the catalyst layer being located immediately at gas access. Being referred to as the second catalyst layer from gas outlet direction at the first catalyst layer catalyst layer subsequently, ensuing catalyst layer is the 3rd catalyst layer. And continue catalyst layer followed by and be denoted as the four, the 5th and the 6th optional catalyst layer. 6th and last catalyst layer of the antigravity system with total of six catalyst layer are located immediately at gas outlet.
When altogether only having the catalyst of three layers, before only the catalyst layer of an antimony content minimizing is placed in the catalyst layer with the highest hot spot, therefore the former is located immediately at gas access. Except this first catalyst layer reduces except antimony content, catalytic active substance (=active substance) content is it is also preferred that be equal to and be particularly preferably less than the activity substance content of second catalyst layer with the highest hot spot. Second go downstream that arrange and catalyst layer closer to gas outlet follows directly after in the first catalyst layer being positioned at gas access, and the antimony content of active substance is corresponding higher. When having the catalyst of total of three catalyst layer, this second catalyst converter layer has the highest hot spot. Ensuing the 3rd catalyst layer more posteriorly arranged that goes downstream is closest to gas outlet, and its activity is usually above the second catalyst layer. The antimony content of last catalyst layer can be equal to, less than or greater than the antimony content of the second layer. To the possible method of the Active Regulation of each catalyst layer known by professional person, wherein, various different measure can be used. The activity of last catalyst layer is improved usually by reducing the accelerator content weakening activity and/or reducing the higher BET surface area content of the titanium dioxide used and/or by adding the accelerator increasing activity and/or being realized by higher activity substance content.
When having the catalyst of total of four layer, one or two antimony contents reduce by the catalyst layer of 20% to 100% and go forward to be placed in the catalyst layer with the highest hot spot preferably in direction, gas access. If the catalyst layer only having an antimony content reduction is preposition in the catalyst layer with the highest hot spot, then the activity substance content of this catalyst layer is equal to or is particularly preferably less than the catalyst layer with the highest hot spot, but unrelated with its activity. In the case, having two rearmounted catalyst layers according to the catalyst layer with the highest hot spot of the present invention on gas outlet direction, wherein, the activity of these catalyst layers preferably increases along gas outlet direction.
Having in the embodiment of total of four catalyst layer at another, the catalyst layer of two Sb content minimizings is preposition in the catalyst layer with the highest hot spot. Antimony content can be inconsistent herein. Preferable case is, wherein the antimony content of a catalyst layer is lower than the antimony content of the catalyst layer with the highest hot spot, it is particularly preferred that situation be that the antimony content of two catalyst layers is below the antimony content with the catalyst layer of the highest hot spot. The catalyst layer in the present embodiment with the highest hot spot is the 3rd catalyst layer, closest to gas outlet the 4th catalyst layer after which.
In the catalyst situation with total of five layer, there is multiple different choice, can have one, two or three catalyst layers go forward to be placed in the catalyst layer with the highest hot spot in direction, gas access. According to the teachings of the present invention, the antimony content of only one catalyst layer in precatalyst layer is only needed to reduce, especially preferred situation is, this preposition catalyst layer filling is highly also the highest, and contained activity substance content is equal to or less than the activity substance content of the catalyst layer with the highest hot spot. The catalyst layer Sb content that particularly all three is preposition all reduces, and the activity substance content that two of which (loads) catalyst layer highly the highest is low. Especially preferred situation is, in the active substance of the catalyst layer that all three is preposition, Sb content and activity substance content all reduce.
For having the catalyst of five catalyst layers, the quantity according to precatalyst layer, one, two or three catalyst layers can be placed on the catalyst layer with the highest hot spot respectively in gas outlet direction. Rearmounted catalyst layer generally increases along gas outlet's direction activity, and this point as described above, can be realized by many kinds of measures. Herein referred to as the 5th catalyst layer the catalyst layer closest to gas outlet generally in all layers activity the highest.
Preferable case is, in the catalyst with total of five catalyst layer, only have a catalyst layer preposition in the catalyst layer with the highest hot spot, the Sb content of this catalyst layer is than the Sb content low 20% to 100% of the catalyst layer with the highest hot spot, and activity substance content is equal to or is preferably shorter than the activity substance content of the catalyst layer of the highest hot spot simultaneously. In embodiments of the invention, three different catalyst layers are placed on the catalyst layer with the highest hot spot. In a preferred embodiment, the second catalyst layer increases to the activity of the 5th catalyst layer along gas outlet direction. And the activity of the first preposition catalyst layer can more than, less than or equal to the activity of second catalyst layer with the highest hot spot.
Especially preferred situation is, in the catalyst with total of five catalyst layer, is provided with two preposition catalyst layers, and its antimony content and active substance all reduce. At this, according to the present invention, the first catalyst layer being arranged at gas access has activity minimum in all catalyst layers, and has the Sb-content reducing 20%-100% relative to the catalyst layer with the highest hot spot simultaneously. Second precatalyst layer preferably activity is higher than the first catalyst layer, and the second precatalyst layer is relative to the catalyst layer with the highest hot spot, and Sb content reduces 20% to 100%, and activity substance content is same or lower in contrast. The activity of two catalyst layers being placed on the catalyst layer with the highest hot spot preferably increases along gas outlet direction. Especially preferred situation is, catalyst layer last on gas outlet direction has significantly high activity.
Broader selection is correspondingly there will be, these optimizations selecting to relate to the principle of the invention in the catalyst situation with total of six catalyst layer. Substantially relate to activity and selective finely regulating herein.
For having the catalyst of total of six catalyst layer, four catalyst layers can be had at most preposition in the catalyst layer with the highest hot spot. The composition of preposition catalyst layer and activity can differ completely. The catalyst of the present invention only needs to meet following condition: preposition reduce by 20% to 100% in the Sb content in the catalyst layer of catalyst layer of the highest hot spot with only one layer, and the activity substance content that the activity substance content of this precatalyst layer is compared with the catalyst layer with the highest hot spot is identical or preferably lower. This catalyst layer is the highest preferably in packed height in all precatalyst layers.
In a preferred embodiment, in the catalyst with total of six layer of the present invention, only have a catalyst layer preposition in the catalyst layer with the highest hot spot. According to the present invention, this precatalyst layer Sb content reduction by 20% to 100% and activity substance content are identical with the activity substance content of the catalyst layer with the highest hot spot. Preferable case is, activity substance content is less than the activity substance content of the catalyst layer with the highest hot spot. The catalyst layer with the highest hot spot of this catalyst is the second catalyst layer defined above. Four rearmounted catalyst layers are preferably stepped up along gas outlet direction. It is distinctive in that chemical composition and/or physical property and/or activity substance content between these rearmounted catalyst layers.
In a particularly preferred embodiment, having in the catalyst of total of six catalyst layer, the catalyst layer that two antimony contents and activity substance content reduce is preposition in the catalyst layer with the highest hot spot. The the first catalyst layer activity in all catalyst layers being located immediately at gas access is minimum, and preferably its activity substance content is also minimum. According to the present invention, the second catalyst layer activity is higher than the first catalyst layer, and preferred activity substance content is also above the first catalyst layer. Meanwhile, antimony content is preferably shorter than the antimony content 20% to 100% of the catalyst layer with the highest hot spot, and activity substance content is equal to or is preferably shorter than the activity substance content of the catalyst layer with the highest hot spot. The activity of this second catalyst layer is smaller than or is preferably greater than the catalyst layer with the highest hot spot being connected to behind. In a preferred embodiment, three catalyst layers being placed on the catalyst layer with the highest hot spot along gas outlet direction are stepped up to activity along gas outlet direction. Especially, last catalyst layer activity is high especially, and activity substance content be optionally below the catalyst layer with the highest hot spot activity substance content and/or on upstream direction the activity substance content of the direct preposition catalyst layer in it.
If surprisingly it has been found that relative to have the catalyst layer distance gas access of maximum temperature extreme value closer to single or some catalyst layer in generate without extra hot spot, then be advantageous for. The precatalyst layer that these Sb content reduces is formed so-called secondary hot spot and selectivity of catalyst and service life will be produced harmful effect.
Respectively according to the type of the catalyst only with the precatalyst layer that a Sb content reduces of the present invention and composition, it is positioned at the first catalyst layer of gas access, namely preposition in the catalyst layer of the catalyst layer with the highest hot spot, its filling is highly 10 to 90cm, it is preferable that filling is highly 20 to 70cm. If only having a catalyst layer in gas access side disposed forwardly of the catalyst layer with the highest local temperature limit, then the filling of this catalyst layer is highly especially preferably 30 to 60cm.
In order to realize best selective and the stability of catalyst, it is preferable that need in situation to coordinate between the activity and packed height of this preposition catalyst layer. Precatalyst layer activity is lower, and the packed height of this precatalyst layer can chosen be then higher. Primary and foremost purpose is, maximum hot spot is present in the catalyst layer that followed antimony content is higher all the time. On the other hand, the total height of the packed height used must guarantee that the reacting gas of reactor exit converts completely.
According to particularly preferred embodiment of the present invention, using two catalyst windrows before having the catalyst layer of the highest local temperature extreme value, wherein, the total fill able of two precatalyst layers is highly preferred is 15 to 90cm, it is particularly preferred that be 30 to 70cm.
If two catalyst layers are positioned at before the catalyst layer with maximum temperature extreme value on direction, gas access, then favourable situation is, the the first catalyst layer packed height arranged closest to gas access is 5 to 25cm, and its activity in all catalyst layers is minimum. Especially advantageous situation is, the packed height of this first catalyst layer is chosen as 5 to 15cm. This minimum sluggish first catalyst layer of activity is lighted running into catalyst windrow beginning for avoiding the raw material not evaporated completely. Therefore, the operational stability of phthalic anhydride preparation method it is remarkably improved by this antigravity system.
In a preferred embodiment, the packed height of the second precatalyst layer is 20 to 60cm, is 30 to 50cm in an especially preferred embodiment.
The packed height of each catalyst layer is crucial to be determined by the total packed height of reaction tube, and the total packed height of reaction tube is determined by pipe range. According to prior art, total packed height is currently chosen as 2.80 to 3.40m mostly.
In a preferred embodiment, the packed height with the first catalyst layer of the catalyst of total of four catalyst layer is 30 to 60cm, the packed height that second catalyst layer (has the catalyst layer of the highest hot spot) is 80 to 150cm, the packed height of the 3rd catalyst layer is 40 to 100cm, and the packed height of the 4th catalyst layer is 40 to 100cm. Especially preferred situation is, the packed height of the first catalyst layer is 30 to 50cm, and the packed height of the second catalyst layer is 90 to 130cm, and the packed height of the 3rd catalyst layer is 50 to 80cm, and the packed height of the 4th catalyst layer is 50 to 80cm.
Have in the catalyst of total of five catalyst layer, preferable case is, according to the total packed height used, the packed height of the first catalyst layer is 5 to 15cm, the packed height of the second catalyst layer is 20 to 50cm, the packed height of the 3rd catalyst layer (hot spot) is 80 to 130cm, and the packed height of the 4th catalyst layer is 50 to 100cm, and the packed height of the 5th catalyst layer is 50 to 100cm.
It is preferable to carry out in flexible program at one of the catalyst with total of six catalyst layer, the packed height of the first catalyst layer is 5 to 15cm, the packed height of the second catalyst layer is 30 to 50cm, the packed height that 3rd catalyst layer (has the catalyst windrow of the highest hot spot) is 80 to 130cm, the packed height of the 4th catalyst layer is 40 to 60cm, the packed height of the 5th catalyst layer is 60 to 80cm, and the packed height of the 6th catalyst layer is 50 to 70cm.
Dissimilar according to PSA catalyst used in the present invention respectively, the activity of the catalyst layer on direction, gas access is smaller than and/or more than the activity of the catalyst layer with maximum local temperature extreme value.
The activity being positioned at the single or some catalyst layer after the windrow with maximum temperature extreme value is typically larger than the catalyst layer with maximum temperature extreme value, and wherein, catalyst layer activity increases along gas outlet direction by catalyst layer.
Especially preferred situation is, the catalyst layer arranged closest to gas access has activity low especially, thus the operational stability of phthalic anhydride preparation method can be improved. Professional person knows, and industry phthalic anhydride equipment is often blasted at reactor inlet place, is especially prone to when load reactor is higher occur. Its reason is contacting for the droplets of feed do not evaporated completely and catalyst windrow beginning often. Thus causing the local pole high capacity of catalyst windrow section start on each catalyst ring, now, if the catalyst activity being positioned at reactor inlet is too high, then " out of hand " condition can be caused. In order to avoid there is above-mentioned lighting, the relatively low catalyst of activity or inactive ceramic body can be used, but, wherein, the windrow being positioned at gas access under latter event is not involved in reaction, and raw material does not convert in this part of windrow. The shorter old-fashioned reactor of pipe range is then in existing defects in this respect, and reason is that residue length remaining, by the pipe of catalyst filling is no longer enough to ensure that raw material converts completely or is no longer enough to ensure that enough product qualities.
Preferably by design of scheme catalyst layer shown below activity:
AK (L1) < < AK (L2) < /=/ > AK (L3) < AK (L4) < AK (L5) < AK (L6)
AK=catalyst layer activity; Li=i-th catalyst layer
For example, professional person can reduce catalyst layer activity by following conventional measure:
-reduce activity substance content, and/or
-reduce the TiO used2Average BET surface area, and/or
-improve caesium content, and/or
-reduce catalyst windrow density, and/or
-mix inert material, and/or
-improve the accelerator content weakening activity, and/or
The accelerator content of-reduction enhanced activity, and/or
-reduce V2O5Content, and/or
-improve antimony content
Or two or more above-mentioned combined measures are used.
In the preferred embodiments of the invention, use unconventional measure to regulate activity and selectivity, the task of the relevant catalyst layer in the position being specifically dependent upon in catalyst bed each catalyst layer and each catalyst layer total backlash (Gesamtspiel).
Preferable case is, the active substance chemical composition of each catalyst layer is different and/or physical property is different. Thus not distinguishing each catalyst layer merely by its different activity substance content.
The preparation method of each catalyst layer and respective composition are known by professional person.
Find within the scope of the present invention, in order to improve selectivity relative to conventional and known catalyst when same stable operation and high raw material are passed through to measure, it is possible to each catalyst layer with special nature and composition is combined use in an advantageous manner.
In a preferred embodiment of catalyst according to the invention, distribute the activity substance content of each layer as shown below:
| AM (L1) < < AM (L2) < AM (L3) < AM (L4) < /=AM (L5) > AM (L6) |
AM: activity substance content; Li=i-th catalyst layer
According to the present invention, for multi-layer catalyst, favourable situation is, described in catalyst as described in the present invention, according to the length of each layer in catalyst bed and position, activity substance content is carried out classification respectively.
For having the catalyst of total of six catalyst layer, the classification of activity substance content is such as follows:
Have been found that favourable situation is, in order to avoid when incomplete evaporation owing to the very high material concentration in local causes that mixture is lighted, the first catalyst layer activity substance content is extremely low. The second preferred activity substance content of catalyst layer is apparently higher than the first catalyst layer, and especially preferred is that the second catalyst layer activity substance content is lower than the catalyst layer with the highest hot spot. The activity substance content with the catalyst layer of the highest hot spot is preferably intermediate value, thus both can guarantee the guide properly to hot spot when high capacity, the raw material of the overwhelming majority can be changed again, and then in the active catalyst layer that downstream is connected to thereafter, not aoxidize the raw material of notable share.
In example catalyst, in order to final lion's share ground converts raw material, it is next to the activity substance content of the catalyst layer after there is the catalyst layer of the highest hot spot and activity is above the catalyst layer with the highest hot spot. Wherein the activity substance content in the two catalyst layer is roughly the same, and closer to the activity of catalyst layer of hot spot catalyst layer lower than the catalyst layer being connected to behind. This kind of activity promotes can such as be reached by other measure known by professional person, it is preferable that by the reduction of caesium content. In order to keep by-product level for low as far as possible, the 6th last, to be positioned at gas outlet catalyst layer activity is high. According to the present invention, the activity substance content of this last catalyst layer is lower than having the catalyst layer of the highest hot spot and/or being located immediately at the catalyst layer in its front. If having been found that, the activity height of the catalyst layer being positioned at QI KOU outlet and activity substance content are also high, then will cause that integer catalyzer selectivity reduces.
According to a preferred embodiment, there are two catalyst layers in the multi-layer catalyst of total of six catalyst layer preposition in the catalyst layer with the highest hot spot, the activity substance content of the first catalyst layer is 3 weight % to 10 weight %, it is particularly preferred that be 3 weight % to 6 weight %. The activity substance content of the second catalyst layer is preferably 4 weight % to 11 weight %, it is particularly preferred that be 5 weight % to 9 weight %. Have been found that the activity substance content of the catalyst layer with the highest hot spot is preferably 5 weight % to 12 weight %, it is particularly preferred that be 6 weight % to 11 weight %, be more preferably 7 weight % to 9 weight %. In a preferred embodiment, the activity substance content of the 4th and the 5th catalyst layer is 5 weight % to 15 weight %, is especially 6 weight % to 12 weight %, is especially 7 weight % to 11 weight %.
In a preferred embodiment, the activity substance content closest to the last catalyst layer of gas outlet is 4 weight % to 11 weight %, and especially preferred is 5 weight % to 10 weight %.
And following catalyst; namely activity substance content keeps catalyst that is equal and/or that reduce and/or increase from the catalyst layer containing the highest hot spot to the catalyst layer being positioned at gas outlet; fall within protection domain; reason is in that; the activity of the catalyst layer being especially placed on the catalyst layer with the highest hot spot can be realized by various modes, and selectivity significantly can't be caused to reduce.
The active substance of each catalyst layer can such as have different chemical compositions. As an alternative or supplement, each catalyst layer, especially be first and second preposition catalyst layer, it is possible to be only distinctive in that activity substance content difference.
In a preferred embodiment of catalyst according to the invention, the main component of each catalyst layer is at least the vfanadium compound in the titanium dioxide of anatase modifications form and active substance. In addition, it is common to use antimonial, especially for using antimony oxide to promote heat stability and the service life of catalyst. Additionally, use cesium compound as improving selectivity and weakening active component in the catalyst of the present invention. Favourable way is, especially uses phosphorus compound to improve activity in the catalyst layer being arranged in gas outlet uses.
In a preferred embodiment of catalyst according to the invention, the antimony content of the first catalyst layer in two catalyst layers is 0 weight % to 2.5 weight %, is especially 0 weight % to 1.5 weight %, it is particularly preferred that being 0 weight % to 1 weight %, it is as Sb2O3Calculating, wherein, this content reduces 20% to 100% preferably with respect to the antimony content of the active substance of the catalyst layer with the highest hot spot.
In the preferred embodiment according to the present invention, the antimony content with the catalyst layer of the highest hot spot is 0 weight % to 5 weight %, is especially 1 weight % to 4 weight %, it is particularly preferred that be that 1.5 weight % to 3.5 weight % is (as Sb2O3Calculate).
In a preferred embodiment of catalyst according to the invention, the antimony content being placed in the catalyst layer after having the catalyst layer of the highest hot spot raises first further along gas outlet direction, it is preferably 0 weight % to 5 weight %, it is particularly preferred that be that 1.5 weight % to 4 weight % is (as Sb2O3Calculate). And the antimony content of rearmounted (some) catalyst layers falls within the scope of the invention less than or equal to the catalyst of hot spot catalyst layer antimony content.
According to the present invention, the antimony content closest to the last catalyst layer of gas outlet reduces relative to catalyst layer before, and its antimony content is preferably 0 weight % to 4 weight %, it is particularly preferred that be 0 weight % to 3.0 weight %.
Therefore, catalyst according to the invention preferably has structurized classification in the antimony content aspect of catalytic active substance, thus completing the different task of each catalyst layer.
In a preferred embodiment, the catalyst layer after being placed in this hot spot catalyst layer also contains stibium oxide. If only having a catalyst layer to be placed on the catalyst layer with the highest hot spot on gas outlet direction, then the antimony content of this rearmounted catalyst layer is preferably equal to or is particularly preferably less than the antimony content of the catalyst layer with the highest hot spot.
Have total of five catalyst layer (catalyst layer that a preposition antimony content reduces and three rearmounted catalyst layers) catalyst according in the preferred embodiments of the invention, antimony content advantageously increases continuously to the 4th catalyst layer from the first catalyst layer, and the antimony content being positioned at the last catalyst layer of gas outlet reduces.
Have total of six catalyst layer (two precatalyst layers and three rearmounted catalyst layers) catalyst according in particularly preferred embodiment of the present invention, the antimony content of the first two catalyst layer is identical, antimony content increases to the 5th catalyst layer step by step from the second catalyst layer, and the antimony content of last catalyst layer reduces. Different antimony contents is mainly used in controlling the selectivity of each catalyst layer, and is not intended to control activity, and reason is in that the activity of catalyst is only had low impact by stibium oxide. In a preferred embodiment, the stibium oxide content of all catalyst layers is 0 weight % to 5 weight %, it is particularly preferred that be 0 weight % to 3.5 weight %. Present invention also contemplates that such catalyst: hot spot catalyst layer antimony content is the highest, in the middle part of rearmounted catalyst layer, the antimony content of divided catalyst layer is lower than the antimony content of the active substance of hot spot catalyst layer, and the antimony content of partially catalyzed oxidant layer is higher than the antimony content of the active substance of hot spot catalyst layer.
As antimony source, it is preferable that select antimony pentoxide, it is particularly preferred that antimony oxide.
If it has been found that the content of vanadium in two catalyst layers above is 2.5 weight % to 9 weight %, it is particularly preferred that be 3 weight % to 6 weight %, then, when o-Dimethylbenzene and/or naphthalene gaseous oxidation being become phthalic anhydride, especially high selectivity can be obtained.
Finding again, according in a preferred embodiment of the present invention, content of vanadium preferably is selected from gas access to gas outlet direction and improves to another catalyst layer from a catalyst layer.
The pentoxide content of the catalyst layer and two preposition catalyst layers with the highest hot spot is preferably 3.5 weight % to 12 weight %, it is particularly preferred that be 4 weight % to 9 weight %.
It has been found that favourable situation is, the content of vanadium of the catalyst layer being positioned at gas outlet is high. Its content of vanadium is advantageously 7 weight % to 25 weight %, it is particularly preferred that be 7 weight % to 22 weight %, particularly 8 weight % to 17 weight %.
As vanadium source, except vanadic anhydride, may select other compounds a series of in principle, for instance vanadium oxalate, halogenation vanadium, metavanadic acid, pyrovanadic acid, carboxylic acid vanadium, such as formic acid vanadium, salicylic acid vanadium or tartaric acid vanadium. Preparing catalyst according to vanadium oxalate is preferably used in embodiment of the present invention.
All catalyst layers of catalyst according to the invention are preferably in other element containing caesium and/or the first main group in active substance.
In a preferred embodiment, caesium content increases from preposition (some) catalyst layers to the catalyst layer with the highest hot spot, and reaches its extreme value in the catalyst layer with the highest hot spot, thus again gradually reducing in rearmounted catalyst layer. In the present invention, caesium content is preferably 0 weight % to 0.7 weight %, it is particularly preferred that be 0 weight % to 0.5 weight %. In an especially preferred embodiment, the preposition caesium content in some catalyst layers is 0.1 weight % to 0.3 weight %.
It is further preferred that do not use phosphorus compound when particularly preparing active substance in preposition layer. In a preferred embodiment, phosphorus content goes downstream to last catalyst layer from the catalyst layer with the highest hot spot and progressively increases, wherein, it is particularly preferred that situation be that the phosphorus content in end layer is apparently higher than the catalyst layer being positioned at sailing against the current before this end layer.
Surprisingly it has been found that favourable situation is, from gas access to the catalyst layer in gas outlet direction (including the catalyst layer with the highest hot spot) containing pucherite. In an especially preferred embodiment, the catalyst layer particularly with the highest hot spot contains pucherite (BiVO in active substance4). According in embodiment of the present invention, the preferred content of the pucherite in active substance is 0 weight % to 4 weight %, is especially 0 weight % to 2 weight %, it is particularly preferred that be 0 weight % to 1.0 weight %. Bismuth compound application in the active substance of the catalyst for preparing phthalic anhydride is early well known (EP0180335A1). Corresponding oxide can be converted into (such as Bi when therefore can be preferably used in calcining2O3) bismuth compound.
According to an aspect of the present invention, bismuth can by the selectivity of gaseous oxidation raising phthalic anhydride product with the mixed oxide of vanadium composition. Its reason is not finally illustrated, but according to estimation, the interaction more preferably in bismuth and the active center of catalyst and especially can make selectivity that the lifting according to the present invention occurs with the interaction more preferably of vanadium species herein.
According to a further aspect in the invention (it is clearly independent of above-mentioned aspect), in catalyst layer at least one (especially in catalyst layer until hot spot catalyst layer or include hot spot catalyst layer) containing silver-colored or silver-colored composition, it is preferably the mixed oxide forms of silver, it is most preferred that for silver vanadate and/or silver molybdate and/or wolframic acid silver. Silver vanadate (AgVO is added in the active substance of one or more catalyst layer in gas access to the catalyst layer (including the catalyst layer with the highest hot spot) with the highest hot spot3) cause improving selectivity. In a preferred embodiment, the silver vanadate content of one or more or all catalyst layers mentioned above is 0.01 weight % to 4 weight %, is especially 0.03 weight % to 2.0 weight %, it is particularly preferred that be 0.05 weight % to 1.0 weight %. These catalyst layers preferably at least also contain titanium dioxide and vfanadium compound in active substance. Active substance is especially preferred also contains at least one alkali metal, it is particularly preferred that for using caesium as the additive improving selectivity and inhibitory activity.
Silver in this case improves selective element, namely by suppressing to occur from o-Dimethylbenzene and/or naphthalene to CO and CO2Complete oxidation.
Now have been surprisingly found that, if according to the present invention by mixed oxide silver metavanadate AgVO3(being not related to so-called silver bronze (Silberbronze)) uses in catalyst preparation process as additive herein, then be remarkably improved selectivity of catalyst. Active substance preferably also at least contains titanium dioxide and vfanadium compound, it is preferred to caesium and/or other element in the first main group, and for having the catalyst layer of the highest hot spot, also extra also have antimonial and/or bismuth compound and/or phosphorus compound.
Active substance compositing range in each catalyst layer is preferably as follows table.
Following table show the form that the exemplary present invention is especially preferred, have the catalyst of total of six catalyst layer, and the 3rd catalyst layer is the catalyst layer with the highest hot spot:
According to a further aspect in the invention, residual activity material is mainly made up of the titanium dioxide of anatase modifications form. In a preferred embodiment, residual activity material at least 90 weight % is made up of titanium dioxide, is especially 95 weight %, it is particularly preferred that be 100 weight %.
Except preferred composition, can also there is other composition in the active substance of one or more catalyst layer according to application target respectively in the catalyst of the present invention. Outside removing carbon dioxide and vanadium oxide, known a series of other compounds (WO99/61433) of professional person also are suitable as the ingredient of active substance, and it is likely to selectivity of catalyst, activity, thermostability and service life to produce actively impact, or it is present in hot spot region as so-called " diluent ".
Art describes a large amount of accelerator, its part also can with in the catalyst of the present invention. Can list for this, alkali metal compound, alkaline earth metal compound, thallium compound, antimonial, bismuth compound, aluminium compound, zirconium compounds, iron compound, nickel compound, cobalt compound, copper compound, manganese compound, tin compound, silver compound, chromium compound, molybdenum compound, tungsten compound, iridic compound, tantalum compound, niobium compound, arsenic compound, cerium compound and phosphorus compound.
Alkali metal compound especially can as weakening activity and raising selectively promotes agent, and selectivity by increased activity, but can be produced harmful effect by phosphorus compound.
In order to especially better reaction is controlled under high capacity, for instance carborundum and other compound such as carbide and nitride also are suitable as in catalyst hot spot region the additive of active substance.
In a preferred embodiment of the catalyst of the present invention, in order to advantageously regulate the activity of each catalyst layer, it is possible to the average surface area using titanium dioxide in different catalysts layer is carried out structuring setting. The average BET surface area of the titanium dioxide of at least one preposition catalyst layer is equal to or more than the average BET surface area of the titanium dioxide of the catalyst layer with maximum hot spot. Situation about being more highly preferred to is, in rearmounted catalyst layer, first the average surface area of titanium dioxide reduces, and in last catalyst layer, the average surface area of titanium dioxide increases. According to aspects of the present invention, not merely by using the titanium dioxide with special properties just the activity of catalyst can be carried out structuring setting, it is possible to used by the combination of the unconventional measure of the part known by professional person and realize.
Professional person also knows, in order to the average BET surface area of the titanium dioxide of a certain catalyst layer is adjusted to desired value, it is possible to use there is expection BET surface area and only a kind of titanium dioxide of other special properties and/or use has the mixture of the long-pending titanium dioxide of different surfaces.
At catalyst according in the preferred embodiments of the invention, in order to the average BET surface area of each catalyst layer is adjusted to desired value, it is possible to use different types of titanium dioxide that BET surface area is different.
The important component part of catalyst according to the invention is BET surface area is 7m2/ g to 50m2The titanium dioxide of the anatase modifications form of/g, BET surface area is preferably 12m2/ g to 30m2/ g, especially preferred surface area is 13m2/ g to 25m2/ g, the average particle size particle size of this titanium dioxide is 0.3 10-6M to 0.8 10-6M, this titanium dioxide is preferably actual to be made up of porous granule, and the aggregation that these particles are made up of predecessor substantially is constituted.
It is different from others discussed above titanium dioxide according to catalyst of the present invention is used as surface area, particle size and particle structure aspect in principle. Therefore, can use, in some or all catalyst layers, the titanium dioxide that one or more surface area, particle size and porous are different.
In the catalyst with total of five or six catalyst layers, before two catalyst layers are placed in the catalyst layer with the highest hot spot on direction, gas access, especially preferred situation is, the first catalyst layer and the second catalyst layer closest to gas access are compared, and activity substance content is considerably lower and/or average BET surface area may be significantly smaller. Owing to the BET surface area of Manufactured catalyst is almost only dependent upon the titanium dioxide kind of use, so according to a kind of preferred embodiment, the BET surface area of the titanium dioxide of the use of the first catalyst layer or the average BET surface area of titanium dioxide kind are preferably equal to or smaller than the BET surface area of the titanium dioxide of the second precatalyst layer or the average BET surface area of titanium dioxide kind.
In a preferred embodiment, the average BET surface area of the titanium dioxide of the catalyst layer residing for the highest hot spot is preferably equal to and is particularly preferably less than the average surface area of the second catalyst layer.
According to a further aspect in the invention, the average BET surface area of the titanium dioxide being positioned at the intermediate catalytic layer after having the catalyst layer of the highest hot spot on direction of going downstream is preferably equal to or is particularly preferably less than the average BET surface area of the titanium dioxide of the catalyst layer with the highest hot spot.
In a preferred embodiment, closest to the average BET surface area of titanium dioxide of last catalyst layer of gas outlet more than the average BET surface area of the titanium dioxide of the 4th and the 5th catalyst layer, it is preferred to equal to or be especially preferred more than the average BET surface area of titanium dioxide of other catalyst layers all.
Therefore, for an especially preferred catalyst, this catalyst has total of six catalyst layer, and two preposition catalyst layer antimony contents reduce, and in this catalyst, the favourable allocative decision of BET surface area is as follows:
| OF (L1) < /=OF (L2) > /=OF (L3) > OF (L4) > /=OF (L5) < OF (L6) |
OF=BET surface area
Li=i-th catalyst layer
In another preferred embodiment of the present invention, a catalyst has total of five catalyst layer, and two catalyst layers are precatalyst layer, and in this catalyst, the favourable allocative decision of BET surface area is as follows:
| OF (L1) < /=OF (L2) > /=OF (L3) > /=OF (L4) < /=OF (L5) |
In another preferred embodiment of the present invention, a catalyst has total of five catalyst layer, and before a catalyst layer is placed in the catalyst layer with the highest hot spot on direction, gas access, the favourable allocative decision in this catalyst is as follows:
| OF (L1) > /=OF (L2) > /=OF (L3) > /=OF (L4) < /=OF (L5) |
In another preferred embodiment of the present, a catalyst has total of four catalyst layer, it is particularly preferred to before only a catalyst layer is positioned at the catalyst layer with the highest hot spot. The favourable allocative decision of average BET surface area is as follows in this case:
| OF (L1) > /=OF (L2) > /=OF (L3) < /=OF (L4) |
The catalyst of the present invention is also not excluded for using other allocative decision of average BET surface area in principle. The present invention is also not excluded for altogether only having three catalyst layers or the multi-layer catalyst more than six catalyst layers. For these so-called multi-layer catalysts, it is possible to will form more than two before different catalyst layers are placed in the catalyst layer with the highest hot spot and/or by after being placed in the catalyst layer with the highest hot spot more than three catalyst layers.
It is said that in general, catalyst used in the present invention relates to lamella catalyst, in these catalyst, the catalytic active substance shell shape in one or more layer puts on inert carrier. The thickness of catalytic active substance is generally 0.02mm to 0.4mm, it is particularly preferred that for 0.05mm to 0.15mm. It is said that in general, at least most of catalyst layer, it is preferred on the direction that goes downstream, it is arranged in the catalyst layer after there is the catalyst layer of the highest hot spot, there is homogeneous active substance chemical composition.
For these lamella catalysts, catalytic active substance is commonly applied on the carrier material of generally imporosity and inertia at reaction conditions, and described carrier material is such as quartz, pottery, magnesium oxide, stannum oxide, carborundum, rutile, aluminium oxide (Al2O3), aluminium silicate, magnesium silicate (Talcum), Zirconium orthosilicate. or these carrier materials mixture.
The carrier of imporosity as active substance of the especially verified spheroid being advantageously made up of Talcum or particularly ring and inertia. In one preferred embodiment of the catalyst of the present invention, the external diameter of Talcum ring is 5mm to 9mm, and length is 4mm to 8mm, and internal diameter is 3mm to 7mm.
In order to prepare this kind of lamella catalyst, prior art describes multiple suitable method. Herein such as can referring to DE-A1642938 and DE-A1769998. Preferably the precursor compound of the liquid in active substance ingredient or the solution containing organic solvent or suspension and/or above-mentioned substance is sprayed on the carrier material of heated cartridge form in rising temperature, until it reaches the active substance share in intended total catalyst weight. Owing to also needing that the inner side of hollow cylinder is uniformly coated with herein, it is advantageous to use bed process to carry out coated inert carrier (DE2106796).
Loss occurs during in order to avoid being applied to inert carrier by active substance, and the measure in this area is, adds so-called organic bond to the solvent containing catalysis activity ingredient or suspension, it is preferred to copolymer, favourable form is aqueous dispersion. The addition of binding agent is about about 5 weight % to 20 weight % of the solids content of catalytic active substance. When adding above-mentioned binding agent, application temperature is advantageously 50 DEG C to 450 DEG C, it is particularly preferred that be 50 DEG C to 200 DEG C.
It is applied simultaneously to binding agent on carrier material with activity ingredient decompose when filling after catalyst in reacting by heating device, is completely removed in active substance. The additional advantage adding binding agent is in that, active substance is firmly fixed on carrier, all will not cause the loss of active substance due to friction when transporting catalyst and reactor are filled.
Thus the catalyst prepared is preferred for o-Dimethylbenzene or naphthalene or o-Dimethylbenzene/naphthalene mixtures gaseous oxidation being phthalic anhydride.
For this, catalyst used in the present invention is fills up in reaction tube, it is advantageous to from outside by the temperature stabilization of this reaction tube under reaction temperature, for instance carry out equilibrium temperature by salt bath. It is generally 300 DEG C to 450 DEG C in temperature, it is preferred to 320 DEG C to 400 DEG C, it is particularly preferred that be 330 DEG C to 390 DEG C, overvoltage0.1bar to 2.5bar, it is preferable that 0.3bar to 1.5bar, to be generally the speed of 750 to 5000l/h to guide the reacting gas catalyst windrow by having been generated by multiple catalyst layers.
The reacting gas being drawn towards catalyst is generally mixed with aromatic hydrocarbon to be oxidized by the gas (being preferably air) containing molecular oxygen, gas containing molecular oxygen also can contain the reaction demulcent and/or diluent that are suitable for except for oxygen, such as steam, carbon dioxide, sulfur dioxide and/or nitrogen, wherein, gas containing molecular oxygen usually contains: the percent by volume of oxygen is 1% to 100%, it is preferably 2% to 50%, it is especially preferably 10% to 30%, the percent by volume of steam is 0% to 30%, it is preferably 0% to 10%, the percent by volume of carbon dioxide is 0% to 50%, it is preferably 0% to 1%, remainder is nitrogen. for reaction of formation gas, generally 25g/Nm must be added to the gas containing molecular oxygen3-140g/Nm3Hydrocarbon to be oxidized.
Catalyst according to the invention carries out heat treatment or calcining before use in a usual manner. Verified advantageously use catalyst at least 6 hours at least 390 DEG C in the gas (particularly air) containing molecular oxygen, especially be use 12 to 24 hours at 400 DEG C to 430 DEG C. Therefore, favourable situation is, the air capacity used is 0.05Nm3To 1Nm3/ often pipe hour.
Professional person is it is well known that the determination method for parameter of catalyst according to the invention, for instance BET surface area, particle size and catalyst activity etc. Herein can referring for example to WO2006/092304. Particularly the mensuration of catalyst activity must be implemented in measuring (salt temperature) under working condition, after catalyst to be observed has reached its effective maximum activity, just carries out this mensuration for the purpose of contrast.
When using catalyst according to the invention, phthalic anhydride can be prepared by o-Dimethylbenzene and/or naphthalene with high selectivity and high-quality under high loads. Catalyst according to the invention is stable, it is possible to economically phthalic anhydride is carried out commercial production for a long time.
Hereafter will further describe the present invention by embodiment, but the thinking of the present invention will be not limited only to these embodiments.
Embodiment
The preparation of catalyst
Each component of active substance and precursor compound (Verlaufverbindung) thereof are successively taken as solution and/or powder is added in deionized water, it is advantageous to the suspension generated carries out stirring at least 12 hours. Source as the component contained by the catalyst of the present invention, it is advantageous to use titanium dioxide, vanadium oxalate, cesium sulfate, ammonium dihydrogen phosphate, antimony oxide, pucherite and silver vanadate.
Then by organic bond, its form is the aqueous dispersion of vinyl acetate copolymer, adds in aqueous suspension, and the suspension by altogether about 20% to 25% is stirred for 30 minutes.
Be then used by spraying by respective amount containing active substance and/or its precursor compoundAnd the aqueous suspension of organic bond applies to inert carrier (Talcum ring, it is of a size of 7 �� 7 �� 4mm or 8 �� 6 �� 5mm) on, until a certain amount of suspension containing binding agent is applied on ring so that the activity substance content shown in embodiment can be obtained after calcining.
Activity substance content or active substance share (share of the catalytically-active materials without binding agent), in either case based on the share of the catalytic active substance in the overall catalyst weight of the carrier included in each catalyst layer, are measured after calcining 4 hours at 400 DEG C.
It is related to the illustrating based on the average BET surface area (being dried under 150 DEG C of vacuum) of the titanic oxide material used of BET surface area of catalyst or catalyst layer. Professional person it is well known that, the TiO used can be passed through2BET surface area substantially determine the BET surface area of catalyst, can pass through to add other catalytic active component within the scope of some, change BET surface area, be specifically dependent upon amount and the surface area of institute's adding ingredient.
The dosage of the phosphorus composition added when the phosphorus content provided is in an embodiment based on supending. Professional person knows, if the TiO used2Strongly polluted by phosphorus, then will there is deviation in the phosphorus actual content in active substance.
Oxidation reaction
Being filled in the tubular reactor with iron reaction tube by relevant multi-layer catalyst system, its internal diameter is 25mm, and length is 3.7m, reaction tube is washed away by around salt bath, wherein, in the described embodiment, L1 layer is closest to gas access in either case, and L4 layer or L5 layer are closest to gas outlet. Diameter be the thermally protective sleeving center arrangement of 2mm in reaction tube, equipped with for thermometric traction element in thermally protective sleeving. It is that under 340 DEG C to 380 DEG C conditions, load is about 30 to 70g o-Dimethylbenzene/Nm at salt temperature3Air time, have 4Nm per hour3Air from top to bottom through reaction tube.
In order to determine catalytic efficiency data, the reacting gas oil cooled condenser of traverse discharged in autoreaction pipe must be guided, its mode is, especially the phthalic anhydride of formation is substantially completely isolated, and such as the by-product such as benzoic acid, maleic anhydride and 2-benzo (c)-furanone only part is isolated.
By deep fat, the thick phthalic anhydride (PSA) of isolation in condenser is melted, receives, weighs, analyze the content determining phthalic anhydride then through GC.
Thick PSA yield computational methods shown in embodiment are:
Although having deducted the by-product wherein contained in the PSA yield measured, but it being still regarded as thick PSA yield, reason is in that, after generally only Grape berry and distillation being processed, the product of gained is called pure PSA. This is also known by professional person.
Owing to the conversion ratio of o-Dimethylbenzene is always close to 100%, so the thick yield so measured is directly consistent with the selectivity of antigravity system.
Embodiment 1 (comparative example):
Catalyst A (5 layers)
Shown in embodiment 1, the test condition of catalyst A is, load 58 to 61g o-Dimethylbenzene/Nm3Air, salt temperature (SBT) is 350 DEG C to 354 DEG C, and air total amount is 4Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 113.1 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.01 weight %.
Embodiment 2 (according to the present invention)
Catalyst B (5 layers)
The test condition of the catalyst B shown in embodiment 2 is, load 58 to 61g o-Dimethylbenzene/Nm3Air, salt temperature is 347 DEG C to 350 DEG C, and air total amount is 4Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 113.8 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.02-0.03 weight %.
Embodiment 3 (according to the present invention)
Catalyst C (5 layers)
The test condition of the catalyst C shown in embodiment 3 is, load 58 to 63g o-Dimethylbenzene/Nm3Air, salt temperature is 345 DEG C to 347 DEG C, and air total amount is 4Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 114.90 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.03 weight %.
Embodiment 4 (according to the present invention)
Catalyst D (5 layers)
The test condition of the catalyst D shown in embodiment 4 is, load 58 to 64g o-Dimethylbenzene/Nm3Air, salt temperature is 346 DEG C to 347 DEG C, and air total amount is 4.0Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 115.0 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.03 weight %.
Embodiment 5 (according to the present invention)
Catalyst E (5 layers)
The test condition of the catalyst E shown in embodiment 5 is, load 58 to 64g o-Dimethylbenzene/Nm3Air, salt temperature is 346 DEG C to 347 DEG C, and air total amount is 4.0Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 115.7 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.02 weight %.
Embodiment 6 (comparative example)
Catalyst F (4 layers)
This catalyst system is actually the multilayer system with four different layers. At this, this catalyst system also can regard five imaginary coating systems as, and the ground floor being wherein positioned at gas access place is divided into two layers with same composition.
The test condition of the catalyst F shown in embodiment 6 is, load 50 to 65g o-Dimethylbenzene/Nm3Air, salt temperature is 344 DEG C to 347 DEG C, and air total amount is 4.0Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 113.4 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.01 weight %.
Embodiment 7 (according to the present invention)
Catalyst G (4 layers)
The test condition of the catalyst G shown in embodiment 7 is, load 58 to 63g o-Dimethylbenzene/Nm3Air, salt temperature is 346 DEG C to 352 DEG C, and air total amount is 4Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 114.0 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.06 weight %.
Embodiment 8 (according to the present invention)
Catalyst H (4 layers)
The test condition of the catalyst H shown in embodiment 8 is, load 58 to 65g o-Dimethylbenzene/Nm3Air, salt temperature is 346 DEG C to 347 DEG C, and air total amount is 4.0Nm per hour3��
At this, the average thick PSA yield (being 100% based on o-Dimethylbenzene purity) after running in stage is 115.3 weight %, and 2-benzo (c) in thick PSA-furanone content is 0.04 weight %.
Form 1:
The efficiency data of catalyst according to the invention
Can be found by the contrast of embodiment 2 to 5 with comparative example 1, reduce preposition in the antimony having in one or more catalyst layers of catalyst layer of the highest hot spot, be remarkably improved selectivity.
Can be found by the contrast of embodiment 7,8 and comparative example 6, use silver vanadate to be remarkably improved the selectivity of catalyst according to the invention.
Claims (5)
1. for aromatic hydrocarbon catalytic vapor phase oxidation being become the catalyst of aldehyde, carboxylic acid and/or carboxylic acid anhydrides, this catalyst has multiple different catalyst layer, wherein, this catalyst has hot spot catalyst layer and at least one is placed in the catalyst layer before this hot spot catalyst layer, the highest local temperature extreme value based on whole catalyst comes across in this hot spot catalyst layer, it is characterized in that
The catalytic active substance of this hot spot catalyst layer has stibium oxide, stibium oxide content in the catalytic active substance of the catalyst layer that at least one of which is preposition reduces 20 weight % to 100 weight % relative to the stibium oxide content in the catalytic active substance of hot spot Catalytic Layer
Described have stibium oxide content to reduce the phosphorus content that at least one preposition catalyst layer of 20 weight % to 100 weight % has be 0 weight % to 0.3 weight %, relative to the catalytic active substance of this catalyst layer,
The activity substance content of hot spot catalyst layer is 5 weight % to 15 weight %, and wherein, catalytic active substance contains
The vanadium oxide of 3 weight % to 12 weight %, with V2O5Calculate,
The stibium oxide of 1 weight % to 3.5 weight %, with Sb2O3Calculate,
The alkali of 0 weight % to 0.8 weight %, calculates with alkali metal,
The phosphorus of 0 weight % to 0.6 weight %, calculates with P,
The bismuth of 0 weight % to 4.0 weight %, calculates with Bi,
The niobium oxide of 0 weight % to 4 weight %, with Nb2O5Calculate,
The silver of 0 weight % to 5.0 weight %, calculates with Ag,
Wherein, remaining as titanium dioxide, and
At least one catalyst layer is upwards placed in side, gas access to be had in whole catalyst before the hot spot catalyst layer of the highest local temperature extreme value, wherein,
A) in the situation of the preposition catalyst layer of only one, stibium oxide content relative to the catalytic active substance of hot spot catalyst layer, the stibium oxide content of the catalytic active substance of this preposition catalyst layer reduces 20 weight % to 100 weight %, wherein the activity of the catalyst layer that this only one is preposition is less than the activity of hot spot catalyst layer
Or
B) in the situation of multiple preposition catalyst layers, stibium oxide content relative to the catalytic active substance of hot spot catalyst layer, in these preposition catalyst layers, the stibium oxide content of at least one of catalytic active substance reduces the value set in advance of 20 weight % to 100 weight %, and wherein this has stibium oxide content and reduces activity that at least one preposition catalyst layer of 20 weight % to 100 weight % the has activity less than hot spot catalyst layer.
2. catalyst according to claim 1, it is characterised in that this has stibium oxide content and reduces the content of vanadium of at least one preposition catalyst layer of 20 weight % to 100 weight % with V2O5It is calculated as 0 weight % to 9 weight %, relative to the catalytic active substance of this catalyst layer.
3. catalyst according to claim 1, it is characterized in that, this alkali content with at least one preposition catalyst layer that stibium oxide content reduces 20 weight % to 100 weight % is calculated as 0 weight % to 0.6 weight % with alkali metal, relative to the catalytic active substance of this catalyst layer.
4. catalyst according to claim 1, it is characterized in that, at least one catalyst layer is placed in after hot spot Catalytic Layer on gas outlet direction, and wherein, in these at least one rearmounted catalyst layers, at least one of activity is higher than the activity of hot spot catalyst layer.
5. catalyst according to claim 1, it is characterised in that use the titanium dioxide kind of anatase modifications form at least one of described catalyst layer, wherein
Using the titanium dioxide kind of anatase modifications form at least one of catalyst layer, its BET surface area is 2m2/ g to 15m2/g��
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008007450.0 | 2008-02-01 | ||
| DE102008007450 | 2008-02-01 | ||
| DE102008011011.6 | 2008-02-25 | ||
| DE102008011011A DE102008011011A1 (en) | 2008-02-01 | 2008-02-25 | Catalyst for the catalytic gas-phase oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and / or carboxylic anhydrides, in particular to phthalic anhydride |
| PCT/EP2009/000534 WO2009095216A2 (en) | 2008-02-01 | 2009-01-28 | Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to form aldehydes, carboxylic acids and/or carboxylic acid anydrides, in particular phthalic acid anhydride |
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| Publication Number | Publication Date |
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| CN101939104A CN101939104A (en) | 2011-01-05 |
| CN101939104B true CN101939104B (en) | 2016-06-01 |
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| Country | Link |
|---|---|
| EP (1) | EP2247384A2 (en) |
| KR (1) | KR101620949B1 (en) |
| CN (1) | CN101939104B (en) |
| BR (1) | BRPI0905796A2 (en) |
| DE (1) | DE102008011011A1 (en) |
| TW (1) | TWI466719B (en) |
| WO (1) | WO2009095216A2 (en) |
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| DE102008044890B4 (en) * | 2008-08-29 | 2023-09-14 | Stesatec Gmbh | Catalyst for the catalytic gas phase oxidation of aromatic hydrocarbons to aldehydes, carboxylic acids and/or carboxylic anhydrides, in particular to phthalic anhydride, and process for producing such a catalyst |
| DE102009041960A1 (en) | 2009-09-17 | 2011-04-07 | Süd-Chemie AG | Process for preparing a catalyst arrangement for the production of phthalic anhydride |
| DE102010012090A1 (en) * | 2010-03-19 | 2011-11-17 | Süd-Chemie AG | Process for the catalytic gas phase oxidation of hydrocarbons and catalytic reaction apparatus |
| WO2015162227A1 (en) | 2014-04-24 | 2015-10-29 | Clariant International Ltd | Catalyst arrangement with optimized void fraction for the production of phthalic acid anhydride |
| DE102014005939A1 (en) | 2014-04-24 | 2015-10-29 | Clariant International Ltd. | Catalyst arrangement with optimized surface for the production of phthalic anhydride |
| EP3047904A1 (en) | 2015-01-22 | 2016-07-27 | Basf Se | Catalyst system for oxidation of o-xylene and/or naphthalene to phthalic anhydride |
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| DE102004014918A1 (en) * | 2004-03-26 | 2005-10-13 | Basf Ag | Catalyst with a silver vanadium oxide phase and a promoter phase |
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- 2009-01-17 TW TW98101757A patent/TWI466719B/en active
- 2009-01-28 KR KR1020107018613A patent/KR101620949B1/en active IP Right Grant
- 2009-01-28 EP EP09707013A patent/EP2247384A2/en not_active Withdrawn
- 2009-01-28 CN CN200980103798.XA patent/CN101939104B/en active Active
- 2009-01-28 BR BRPI0905796A patent/BRPI0905796A2/en not_active Application Discontinuation
- 2009-01-28 WO PCT/EP2009/000534 patent/WO2009095216A2/en active Application Filing
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| DE102004014918A1 (en) * | 2004-03-26 | 2005-10-13 | Basf Ag | Catalyst with a silver vanadium oxide phase and a promoter phase |
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| DE102008011011A1 (en) | 2009-08-06 |
| BRPI0905796A2 (en) | 2016-06-21 |
| KR20100111299A (en) | 2010-10-14 |
| CN101939104A (en) | 2011-01-05 |
| TWI466719B (en) | 2015-01-01 |
| WO2009095216A2 (en) | 2009-08-06 |
| EP2247384A2 (en) | 2010-11-10 |
| KR101620949B1 (en) | 2016-05-13 |
| WO2009095216A3 (en) | 2010-04-29 |
| TW200946225A (en) | 2009-11-16 |
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