Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
  • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
  • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
• • 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
  • B01J23/32—Manganese, technetium or rhenium
  • B01J23/34—Manganese
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
  • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
  • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
  • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/32—Manganese, technetium or rhenium
  • C07C2523/34—Manganese
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• This invention relates to lower alkane oxidative dehydrogenation catalysts and a production process of olefins using said catalysts. More specifically, the invention relates to the catalysts which are suitable for use in vapor phase oxidative dehydrogenation of C 2 -C 5 lower alkanes (hereinafter occasionally referred to simply as “lower alkanes”) in the presence of molecular oxygen to produce corresponding olefins, and a process for oxydizing and dehydrogenating lower alkanes with molecular oxygen to produce corresponding olefins at high yields, with the use of said catalysts.
• lower alkanes C 2 -C 5 lower alkanes
• the invention also relates to a process for producing, from the olefins which have been obtained through vapor phase oxidative dehydrogenation of C 2 -C 5 lower alkanes in the presence of molecular oxygen, the corresponding unsaturated aldehydes and/or unsaturated carboxylic acids.
• Japanese Laid-open (KOKAI) Patent Application, KOKAI No. 245494/1996 furthermore contains a disclosure on a process for further oxidizing propylene, which was formed through dehydrogenation of propane, to produce acrylic acid. This process, however, necessitates removal of the hydrogen formed during the dehydrogenation of propane from the reaction gas.
• Japanese KOKAI Nos. 045643/1998, 118491/1998, 62041/1980 and 128247/1992, etc. disclose processes for forming unsaturated aldehydes and/or acids from lower alkanes, in particular, acrolein and/or acrylic acid from propane and methacrolein and/or methacrylic acid from isobutane.
• yield of these object products indicated in these publications are very low, and the processes need to be improved in various aspects including the catalyst to be used.
• An object of this invention is to provide novel oxidative dehydrogenation catalysts useful for vapor phase oxidative dehydrogenation of lower alkanes with molecular oxygen to produce corresponding lower olefins at high yield; and also to provide a process for producing from lower alkanes the corresponding olefins at high yield, by the use of said catalysts.
• Another object of the invention is to provide a process for producing from lower alkanes corresponding unsaturated aldehydes and/or unsaturated carboxylic acids at high yield.
• the present invention provides catalysts for oxidative dehydrogenation of lower alkanes, said catalysts being suitable for use in vapor phase oxidative dehydrogenation of C 2 -C 5 lower alkanes in the presence of molecular oxygen to produce corresponding olefins and characterized by having a composition expressed by a general formula (I) below:
• Mn denotes manganese, and O, oxygen
• E 1 is at least one element selected from the group consisting of P, As, Sb, B, S, Se, Te, F, Cl, Br, I, Nb, Ta, W, Re and Cu
• E 2 is at least one element selected from the group consisting of Cr, Fe, Co, Ni, Ag, Au, Zn, Tl, Sn, Pb, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Y, La, Ce, Nd and Sm
• the present invention furthermore provides a process for producing olefins which comprises vapor phase oxidative dehydrogenation of C 2 -C 5 alkanes in the presence of molecular oxygen to form corresponding olefins, characterized by the use of the above-described catalyst.
• a process for producing, from lower alkane, unsaturated aldehyde and unsaturated acid at high yield in which an olefin obtained through vapor-phase oxidative dehydrogenation of C 2 -C 5 lower alkanes in the presence of molecular oxygen using the above-defined catalyst is further oxidized at vapor phase in the presence of oxygen to provide unsaturated aldehyde and unsaturated acid.
• the invention moreover provides a process for producing unsaturated acid from lower alkane at high yield, in which the unsaturated aldehyde obtained as above is further oxidized at vapor phase in the presence of molecular oxygen to provide unsaturated acid.
• C 2 -C 5 lower alkanes signify ethane, propane, n-butane, isobutane, n-pentane and isopentane.
• the catalysts of the present invention are used in oxidative dehydrogenation reactions of these lower alkanes to produce corresponding olefins, more specifically, ethylene from ethane, propylene from propane, n-butene from n-butane, isobutene from isobutane, n-pentene from n-pentane and isopentene from isopentane.
• These lower alkanes may be used either singly or as a mixture of more than one.
• the oxidative dehydrogenation catalysts of the present invention are useful for the production of, in particular, propylene and isobutene from propane and isobutane, respectively.
• the catalysts of the general formula (I) in which E 1 component is P, Sb, B, S, Nb, W or Re and E 2 component is Cr, Fe, Sn, Na, Mg or Ce are preferred.
• the oxidative dehydrogenation catalysts of general formula (I) of the present invention may be used as supported on a refractory inorganic carrier for the purpose of improving activity level and physical durability.
• a refractory inorganic carrier those generally used in preparation of this type of catalysts can be used, the representative examples thereof including silica, alumina, titania, zirconia, silica-alumina, silica-titania and silica-zirconia.
• silica and silica-alumina are preferred, because they give higher yield of object products.
• the ratio of silica in the silica-alumina catalyst system normally ranges from 10% by weight to less than 100% by weight.
• the amount of the catalytically active component to be carried is normally between 10 and 90% by weight of the refractory inorganic carrier.
• the method of preparation of the oxidative dehydrogenation catalysts of the present invention is not subject to any critical limitations, but any of conventionally practiced methods or known methods for preparation of this type of catalysts can be used.
• the catalysts may be prepared by the procedures comprising adding to a slurry of manganese dioxide powder antimony trioxide powder and aqueous solutions of phosphoric acid, boric acid, ammonium sulfate, telluric acid, ammonium chloride, niobium oxalate, ammonium tungstate, rhenium oxide and copper nitrate, etc.
• E 1 component if necessary further adding aqueous solution of at least one element selected from the E 2 component; further if necessary adding a carrier such as silica, alumina or the like thereto; condensing the mixture under heating with agitation for a prescribed period, drying the resultant paste at 80-300° C.; pulverizing and molding the same; if necessary further crushing the same for size adjustment or re-drying at 80-300° C.; and if necessary further firing the dry product at 300-800° C.
• the firing atmosphere is subject to no limitation, and the firing may be conducted in air, an atmosphere of high or low oxygen concentration, a reducing atmosphere, in an inert gas such as nitrogen, helium, argon or the like, or in vacuum.
• the catalyst is not firing at the high temperatures but is contacted with the reaction gas containing the alkane or alkanes and oxygen as it has undergone the drying treatment or treatments at not higher than 300° C.
• the reaction may be started at a temperature not lower than the prescribed level by way of a pre-treating reaction, or directly at the prescribed temperature. In the latter case changes in catalytic activity may be observed at the initial stage of the reaction, but normally a stable activity level is reached within an hour.
• the starting materials for catalyst preparation are not critical, but may be any of nitrate, sulfate, oxide, hydroxide, chloride, carbonate, acetate, oxygen acid, ammonium salt of oxygen acid, etc. of the elements.
• Mn source besides powders of various oxides thereof or molded products which are useful as they are, manganese hydroxide slurries obtained upon treating an aqueous solution of, eg., manganese nitrate, with aqueous ammonia or the like are conveniently used. Any means used for catalyst preparation in general, for example, co-precipitation of a manganese compound with compounds of other additive elements from their aqueous solution, are applicable.
• sulfur source aqueous sulfuric acid or ammonium sulfate may be used, or the whole or a part thereof may be introduced in the form of sulfate(s) of other additive element(s).
• halogen may be introduced as aqueous hydrogen halide or ammonium halide, or in the form of halide(s) of other additive element(s).
• refractory inorganic carrier is subject to no critical limitation, which allows versatile selection according to the form of use of the catalyst, such as, besides molded products, powder of oxide or hydroxide, gel or sol.
• the starting gas to be subjected to the vapor phase oxidative dehydrogenation reaction according to the present invention may if necessary contain a diluent gas, besides lower alkane(s) and molecular oxygen.
• a diluent gas besides lower alkane(s) and molecular oxygen.
• molecular oxygen air or pure oxygen is used, normally at a ratio of 0.1-5 mols per mol of alkane.
• an inert gas such as nitrogen, helium or carbon dioxide or steam is conveniently used.
• the reaction conditions for carrying out the vapor phase oxidative dehydrogenation of the present invention are subject to no critical limitation.
• the starting gas as described above is contacted with an oxidative dehydrogenation catalyst of the present invention under such conditions as: at a space velocity of 300-30,000 hr ⁇ 1 at a temperature between 250 and 650° C.
• the reaction is normally conducted under atmospheric pressure, a reduced or elevated pressure may be used.
• the reaction system again is not critical, which may be a fixed bed system, moving bed system or fluidized bed system. It may also be one-pass system or recycling system.
• the olefines (alkenes) which are obtained through the vapor phase oxidative dehydrogenation of C 2 -C 5 lower alkanes (alkane oxidative dehydrogenation step) using the catalyst of the present invention can be further oxidized to produce unsaturated aldehydes and unsatuated acids (alkene oxidation step).
• the unsaturated aldehydes can further be oxidized to produce unsaturated acids (aldehyde oxidation step).
• unsaturated aldehydes and/or unsaturated acids are trapped with an absorption column (absorbing step).
• an absorption column absorbing step.
• oxygen source in the present invention air and/or oxygen produced by such methods as cryogenic method, P.S.A.
• Mo molybdenum
• Bi bismuth
• Fe iron
• A is at least one element selected from the group consisting of cobalt and nickel
• B is at least one element selected from the group consisting of alkali metals and thallium
• C is at least one element selected from the group consisting of silicon, aluminium, zirconium and titanium
• D is at least one element selected from the group consisting of tungsten, phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic and zinc
• Mo molybdenum
• V vanadium
• W tungsten
• E is at least one element selected from the group consisting of copper, cobalt, bismuth and iron
• F is at least one element selected from the group consisting of antimony and niobium
• G is at least one element selected from the group consisting of silicon, aluminium, zirconium and titanium
• H is at least one element selected from the group consisting of alkaline earth metals, thallium, phosphorus, tellurium, tin, cerium, lead, manganese and zinc
• the lower alkane oxidative dehydrogenation catalysts according to the present invention excel in the oxidative dehydrogenation ability and enable the production from lower alkanes of corresponding olefins at high yield.
• unsaturated aldehyde and/or unsaturated acid can be produced from lower alkanes stably at high yield.
• Feed rate 112.5 ml/min.
• SV equivalent to 12,000 hr ⁇ 1 (In the subsequent Examples, indication of SV is omitted. As the catalyst weight was constant, SV underwent fluctuation more or less dependent on its packing density.)
• the catalyst preparation was conducted in the same manner as in Example 1, except that the amount of the antimony trioxide powder was changed to 1.82 g.
• the resulting catalyst had a composition of Mn 1 Sb 0.25 Ox. Using 0.6 g of this catalyst, the reaction was conducted under identical conditions with those of Example 1. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 0.58 g of 85% phosphoric acid (H 3 PO 4 , special grade reagent manufactured by Kanto Chemical) as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 P 0.1 Ox.
• the reaction was conducted under identical conditions with those of Example 1, except that the reaction temperature was raised to 490° C. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 3, except that the amount of the 85% phosphoric acid was changed to 1.15 g.
• the resulting catalyst had a composition of Mn 1 P 0.2 Ox. Using 0.6 g of this catalyst, the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 0.31 g of boric acid (H 3 BO 3 , special grade reagent manufactured by Kanto Chemical) as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 B 0.1 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 0.66 g of ammonium sulfate (special grade reagent manufactured by Kanto Chemical) as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 S 0.1 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 1.62 g of niobium oxalate (a product of C.B.M.M. Co., containing 20.5% of Nb 2 O 5 upon conversion) as dissolved in 100 ml of water.
• the resulting catalyst had a composition of Mn 1 Nb 0.05 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 1.16 g of aqueous ammonium meta-tungstate solution, MW-2 (a product of Nippon Inorganic Colour and Chemical Co., LTD., containing 50% of WO 3 ) as diluted with 50 ml of water.
• the resulting catalyst had a composition of Mn 1 W 0.05 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 0.61 g of rhenium oxide (Re 2 O 7 , Kishida Chemical, purity 99.99%) as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 Re 0.05 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 1.21 g of copper nitrate (Wako Pure Chemical Industry LTD., purity 99.9%) as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 Cu 0.1 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 1.07 g of ammonium chloride (special grade reagent manufactured by Kanto Chemical) as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 Cl 0.4 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that 2.00 g of chromium nitrate [Cr(NO 3 ) 3 .9H 2 O, Wako Pure Chemical Industry LTD., purity 99.9%] as dissolved in 50 ml of water was added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 Cr 0.1 Ox.
• the reaction was run under identical conditions with those of Example 1. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that 2.02 g of iron nitrate [Fe(NO 3 ) 3 .9H 2 O, Wako Pure Chemical Industry LTD., special grade reagent] as dissolved in 50 ml of water was added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 Fe 0.1 Ox.
• the reaction was run under identical conditions with those of Example 1. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that 0.42 g of sodium nitrate (Wako Pure Chemical Industry LTD., special grade reagent) as dissolved in 50 ml of water was added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 Na 0.1 Ox.
• the reaction was run under identical conditions with those of Example 1. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that 1.28 g of magnesium nitrate [Mg(NO 3 ) 2 .6H 2 O, Wako Pure Chemical Industry LTD., special grade reagent] as dissolved in 50 ml of water was added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 Mg 0.1 Ox.
• the reaction was run under identical conditions with those of Example 1. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that 2.22 g of cerium nitrate [Ce(NO 3 ) 3 .6H 2 O, Wako Pure Chemical Industry LTD., special grade reagent, purity 98%] as dissolved in 50 ml of water was added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 Ce 0.1 Ox.
• the reaction was run under A identical conditions with those of Example 1. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 1.11 g of chromium sulfate [Cr 2 (SO 4 ) 3 .4H 2 O, Kanto Chemical, first grade reagent] as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 S 0.15 Cr 0.1 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that the antimony trioxide powder was replaced with 1.75 g of stannic chloride (SnCl 4 .5H 2 O, Wako Pure Chemical Industry. LTD., special grade reagent) as dissolved in 50 ml of water.
• the resulting catalyst had a composition of Mn 1 Cl 0.4 Sn 0.1 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that 1.16 g of aqueous ammonium meta-tungstate solution MW-2 as diluted with 50 ml of water and 2.00 g of chromium nitrate as dissolved in 50 ml of water were added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 W 0.05 Cr 0.1 Ox.
• the reaction was run under identical conditions with those of Example 1. The results were as shown in Table 1.
• Example 19 Using 0.6 g of the catalyst which was used in Example 19, the reaction of Example 19 was repeated except that the reaction temperature was raised to 490° C. The results were as shown in Table 1.
• the catalyst preparation was conducted in the same manner as in Example 1, except that 1.16 g of aqueous ammonium meta-tungstate solution as diluted with 50 ml of water and 1.11 g of chromium sulfate as dissolved in 50 ml of water were added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 W 0.05 S 0.15 Cr 0.1 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• Example 21 Using 0.6 g of this catalyst which was used in Example 21, the reaction of Example 21 was repeated except that the reaction temperature was raised to 530° C. The results were as shown in Table 1.
• the catalyst preparation was repeated except that 1.16 g of aqueous ammonium meta-tungstate solution MW-2 as diluted with 50 ml of water, 1.62 g of niobium oxalate as dissolved in 100 ml of water and 2.00 g of chromium nitrate as dissolved in 50 ml of water were added following the addition of the antimony trioxide powder.
• the resulting catalyst had a composition of Mn 1 Sb 0.15 W 0.05 Nb 0.05 Cr 0.1 Ox.
• the reaction was run under identical conditions with those of Example 3. The results were as shown in Table 1.
• Example 23 Using 0.6 g of the same catalyst as used in Example 23, the reaction of Example 23 was repeated except that the reaction temperature was raised to 530° C. The results were as shown in Table 1.
• Example 2 The same manganese dioxide powder as the one used in Example 1 was pulverized, molded and crushed to a uniform size of 9-20 mesh. Using 0.6 g of this catalyst, the reaction was run under identical conditions with those of Example 1. The results were as shown in Table 1.
• Example 1 The reaction of Example 1 was repeated except that 0.6 g the catalyst same to that used in Comparative Example 1 was used and the reaction temperature was raised in 490° C. The results were as shown in Table 1.
• Example 1 450 27.3 27.1 0.3 7.4
• Example 2 450 26.9 26.7 0.7 7.2
• Example 3 490 31.2 33.4 0.3 10.4
• Example 4 490 30.9 33.7 0.3 10.4
• Example 5 490 9.7 47.3 1.4
• Example 6 490 17.9 36.3 0.4 6.5
• Example 7 490 30.3 29.6 0.2 9.0
• Example 8 490 29.7 29.4 0.2 8.7
• Example 9 490 8.4 53.8 0.2 4.5
• Example 10 490 25.3 22.2 0.1 5.6
• Example 11 490 27.1 16.1 0.1 4.4
• Example 12 450 30.0 28.0 0.5 8.4
• Example 13 450 28.1 27.8 0.6 7.8
• Example 14 450 26.5 28.7 0.3 7.6
• Example 15 450 27.4 28.1 0.3 7.7
• Example 16 450 29.2 26.7 0.4 7.8
• Example 17 490 28.8 23.8 0.1 6.9
• Example 18 490 25.5 19.8
• Each independently temperature-controllable single-pipe flow type reactors (A), (B) and (C) were connected in such a manner that gas would flow by the order of (A) to (B) to (C), with the piping so designed that the gas formed in the reactor (C) is introduced into an absorption column to allow absorption of condensed component and introduction of the uncondensed gas flowing out of the absorption column into the reactor A through its gas inlet portion, and the reaction was conducted with the following particulars.
• the piping also was so connected that fresh air could be introduced into the reactor (B) through its gas inlet portion.
• the reactor (C) was packed with 52 g of a catalyst of the following composition (excepting oxygen) as described in Example 1 of Japanese KOKAI No. 206504/1996:
• the flow rates of propane, air and recovered gas from absorption column were so controlled at the gas inlet portion of the reactor (A) as to give the reaction gas composition of 15 vol % C 3 H 8 , 15 vol % O 2 and 70 vol % of inert gases comprising nitrogen, carbon oxide, etc.
• the space velocity to the oxidative dehydrogenation catalyst was 3000 hr ⁇ 1 .
• the product gas from the reactor (A) was fed into the reactor (B) while adding air thereto at such a rate that O 2 /C 3 H 6 ratio therein should become 2.5 at the entrance portion of the reactor (B), and the product gas from the reactor (B) was fed into the reactor (C).
• the reaction temperatures in the reactors (A), (B) and (C) during the run were 480° C., 325° C. and 250° C., respectively.
• the flow rates of propane and gaseous oxygen were so controlled at the gas inlet portion of the reactor (A) as to give the reaction gas composition of 30 vol % C 3 H 8 , 30 vol % O 2 and 40 vol % of inert gases comprising nitrogen, carbon oxide, etc.
• the space velocity to the oxidative dehydrogenation catalyst in that occasion was 4,000 hr ⁇ 1 .
• the product gas from the reactor (A) was fed into the reactor (B) while adding air thereto at such a rate that the O 2 /C 3 H 6 ratio therein should become 1.5 at the gas inlet portion of the reactor (B).
• the product gas from the reactor (B) was fed into the reactor (C), while adding air and steam thereto at such rates that the O 2 /acrolein ratio and steam concentration therein should become 1.3 and 35 vol %, respectively, at the gas inlet portion of the reactor (C).
• Other conditions were identical with those of Example 26.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=15151325

Family Applications (3)

Family Applications After (2)

Country Status (8)

Cited By (4)

Families Citing this family (10)

Family Cites Families (31)

• 1999
  • 1999-05-10 JP JP12844199A patent/JP3678335B2/ja not_active Expired - Fee Related
  • 1999-05-14 SG SG9902446A patent/SG80030A1/en unknown
  • 1999-05-17 ID IDP990453A patent/ID22586A/id unknown
  • 1999-05-17 MY MYPI99001937A patent/MY121416A/en unknown
  • 1999-05-18 CN CN99106660A patent/CN1112967C/zh not_active Expired - Fee Related
  • 1999-05-18 US US09/313,652 patent/US20010008623A1/en not_active Abandoned
  • 1999-05-18 EP EP99303859A patent/EP0963788B1/de not_active Expired - Lifetime
  • 1999-05-18 DE DE69921020T patent/DE69921020T2/de not_active Expired - Lifetime
• 2001
  • 2001-07-02 US US09/895,416 patent/US6756517B2/en not_active Expired - Fee Related
• 2004
  • 2004-02-13 US US10/777,045 patent/US20040162453A1/en not_active Abandoned

Also Published As

Similar Documents

Legal Events