DE2106756A1 - Oxidative dehydrogenation catalysts and processes for their preparation - Google Patents

Description

Petro-Iex Chemical Corporation Houston, Texas / USA

Oxidative dehydrogenation catalysts and processes

for their manufacture

The invention relates to improved dehydrogenation catalysts, processes for their preparation, in particular catalysts for oxidative dehydrogenation and processes using such catalysts.

Many different dehydrogenation catalysts are known. The present invention relates to such dehydrogenation catalysts which contain a metal compound or mixtures of metal compounds. Such connections include metal oxides, metal salts such as the halides, phosphates, sulfates, molybdates, Wblframates, and others in general One can describe these catalysts as compounds that have a metal in a polyoxidation state contain, i.e. a metal that, in addition to the NuIl-Zu3tand has at least two oxidation levels. Suitable

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Metals are in groups IVB, VB, VIB, VIIB, VIII, Ib, IVA, VA and VIA of the Periodic Table of the Elements found (Handbook of Chemistry and Physics, 45th Edition, 1964-1965, The Chemical Rubber Co., Cleveland, Ohio, Page B-2). Particularly valuable metals in a multivalent oxidation state are Ti, V, Cr, Mn, Pe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Sn, Sb, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi and Po. It has been found that the present Process is particularly suitable for the preparation of oxidative dehydrogenation catalysts. Some excellent oxidative dehydrogenation catalysts include tin (IV) phosphate, lead molybdate, aluminum tungstate, Cobalt tungstate, iron oxide, antimony oxide, bismuth molybdate, Chromium oxide, Y / olfactory oxide, vanadium oxide and others.Suitable oxidative Dehydrogenation catalysts can be such a metal, which can be in the polyoxidation state, or Contain mixtures of such metal compounds. Often these catalysts come in different combinations used together, for example lead molybdate / aluminum grinder ramat, lead molybdate / cobalt wolf garnet, iron oxide / Chromium oxide, iron oxide / vanadium oxide, iron oxide / manganese oxide etc.

In addition to the metal, which can be present in many oxidation states (polyoxidative state metal), the invent ungs ge mass en dehydrogenation catalysts contain one or more metals in the mono-oxidation state, which act as activators or promoters, initiators, stabilizers, etc. can act. The metal or metal compounds in simple oxidation state include metals from groups IA, HA, IHB, IVB, VB, VIIB, IB, HB, IHA and IVA, preferably the divalent metals of these groups. Among these are often specific in the oxidative Dehydrogenation catalyst systems Mg, Al, Ca, Sc, Zn, Sr, Cd and Ba found. As in the US patents 3,173,855 and 3,247,278 have been found to be

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Alurainium oxide in the form of natural or synthetic molecular sieves is a particularly effective oxidation dehydrogenation catalyst. The oxidative dehydrogenation catalysts also contain compounds of Be, the lanthanides La, Hf, Ta, Ce, Pr, Nd, Pn, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Di (Di is used to describe a mixture of rare earths, e.g. _{Bi 2} Q ₃ typically contains 45 to 46 $ 1 to 24 _{CeO 2} , 9 Ms 10 $ Pr ₆ O ₁₁ , 32 to 33 ^ Nd ₂ O ₃ , 5 to 6 $ SiQ-O ,, 3 to 4 $ Sd ₀ O- ,, 0,4 / 6 Yb ₀ O, and 1 to 2 $ other rare earths), the actinides (e.g. Th, Pa) ₁ - {

Se, G-a, Y, Zn, Se, Ie and In.

In addition to the metals, the catalysts often contain various non-metallic compounds that act as activators, initiators, stabilizers, etc. In the Orya & tiQiisdohydrieriffigskatalysatoren alkali often ve r *: vtinctungen in "begrarjsten amounts available as Li ₂ O, 3fe _o u and K ₂ O. knarre:> ..: ai; ÄStoff e are sulfur, phosphorus, · 'üilioiuiü ■, Bor or & ei "-...! Ils: hung en * for example '*

iiilfate, sulphites, sulphides, alkyl.tierorvpT.ane- _v sulfuric acid, ^v , f phosphates, phosphoric acid, silica., silicates »boron- ■ •; rii" l "j.orid, etc. Such additives are described in US patents 5 247 278, 3 270 080, 3 303 238, 3 324 195 ": - ^ mL 3 398 100 described."^;

To improve the results, halogen is often present in oxidative dehydrogenation. The presence of. '"Halogen in the dehydrogenation zone is especially effective when the compound to be dehydrogenated is saturated such as a saturated hydrocar-. ^F serstoff. The halogen which is present in the dehydrogenation zone, either elemental halogen or may be ^9" 'a Halogen compound which releases halogen under the reaction conditions - * ''. Suitable sources are hydrogen iodide, % * ■ ". Hydrogen bromide and hydrogen chloride, ethyl iodide, methyl- Y ^- T '^

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bromide, methyl chloride, 1,2-dibroinethane, ammonium iodide, Ammonium bromide, ammonium chloride, sulfuryl chloride, etc. The halogen may be partially or completely from a solid source as described in US Pat. No. 3,130,241. Mixtures of halogen and off Compounds that release halogen can be used * The amount of halogen, calculated as elemental halogen, can be as low as about 0.0001 or less moles of halogen per mole of organic compound that is dehydrogenated v / should be earthed and as much as 0.2 or 0.5. The use of halogens in oxidative dehydrogenation is in U.S. Patents 3,210,436 / 3,207,805, 3 20? 810, 3 277 207, 3 278 626, 3 308 182 - 3 308 200, 3,316,320, 3,356,750, 3,359,343, 3,374,283, 3,382,290, 3,440,298, and 3,442,968.

In addition to the catalysts described above, oxidative dehydrogenation catalysts are used in the following US patents described, which are encompassed by the present invention! 3 420 911 »3 420 912, 3,428,703, 3,440,299, 3,260,767, 3,274,285, 3,284,536, 3 303 234-7, 3 320 329, 3 334 152, 3 336 408, 3 342 890, 3 404 193, 3 437 703, 3 446 869 and 3 456 030.

Among the preferred catalysts according to the invention are those containing iron, oxygen and at least one other metallic element Me. The catalysts include crystalline compositions of iron, oxygen and at least one other metallic element Me. The catalysts include ferrites. In general, the ionic radius of the second metallic component (e) is Me small enough that the oxygen anions are not too far apart. This means that the elements in the Must be able to form a crystalline structure with the iron and oxygen.

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A preferred type of catalyst of this type is one which has a face-centered cubic form of crystalline structure. Examples of this type of catalyst are ferrites of the general formula MeO · FepO ,, v / orin Me is a divalent metal cation such as Mg ++ or Ni ++. However, when the cations are large as Sr ++ (1.35 Å), the spinel structure cannot appear and other kinds of ferrites having a hexagonal crystal of the type SrO · 6Fe ₂ O ₇ can be formed. These hexagonal ferrites are also included in the present invention.

Suitable catalysts can also be ferrites, in which the iron is partially replaced by other metals is. For example, atoms that have a valence of +3 can partially replace some of the Fe +++ atoms. Metal atoms with a valence of +4 can also replace some Fe +++ ions. However, in the Catalysts iron still in a suitable amount as described above in relation to the total atoms of the second metallic Constituent (s) be present.

The catalysts can contain iron, as described above, together with oxygen and more than one other metallic element in a crystalline structure. For example, a preferred type of ferrite is that substantially or approximately of the formula MeFe ^ O. corresponds to where Me is a divalent metal ion with an ionic radius of approximately between 0.5 and 1.1 λ, preferably between approximately 0.6 and 1.0 λ. In the case of simple ferrites, Me can mean, for example, one of the divalent ions of the transition elements such as Mg, Ca, Sr, Ba, Cr, Mn, Co, Ki, Zn or Cd. However, a combination of these ions can also be present, with ferrites such as Ni _n P-Mg _n ^ e ₀ O. or Ni _n ^ Mg _{n 7} cFe ₉ 0 being formed.

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Furthermore , the symbol Me can mean a combination of ions which have an average value of 2. It is essential, however, that the crystalline structure contain iron and that the metallic element be other than iron.

Examples of catalysts are such as magnesium ferrite, Cobalt ferrite, nickel ferrite, zinc ferrite, barium ferrite, strontium ferrite, manganese ferrite, calcium ferrite, Cadmiura ferrite, silver ferrite, zirconium ferrite and ferrite from Rare earths such as Cerferrit or mixtures of ferrites such as ferrites, the iron, combined with at least one Contain element that is selected from the group that contains Mg, Zn, Hi, Co, Mn, Cu, Cd, Ca, Ba, Sr, Al, Cr, Ti, V, Mo, V /, Na, Ii, K, Sn, Pb, Sb, Bi, Ga, Ce, La, Th, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho , He, Tm, Yb, Lu and mixtures thereof, a preferred group being: Mg, Ca, Sr, Ba, Mn, Cr, Co, Ni, Zn, Cd and mixtures thereof and particularly preferred metals are Mg or Mn. Examples of mixed ferrites are magnesium ferrite plus zinc ferrite, magnesium ferrite plus nickel ferrite, Magnesium ferrite plus cobalt ferrite, x-lagnesium ferrite plus nickel ferrite plus zinc ferrite, magnesium ferrite plus manganese ferrite. As described above, these ferrites can physical mixtures of ferrites or they can contain crystals representing the different metal atoms are contained in the same crystal, or they can be a combination of physical mixtures and chemical combinations. Examples of a chemical combination would be magnesium sink ferrite, magnesium chrome ferrite, Zinc chromium ferrite and lanthanum chromium ferrite.

The valence of the metals in the catalysts does not have to have any particular values, although certain combinations are preferred. Determining the valence of the Ions is sometimes difficult and the results are un-

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certainly. The different ions can exist in more than one valence state. However, a "is more preferable Catalyst one in which the iron is predominantly in the Fe +++ state. Some ferrites are in Ferromagnetism by Richard M. Bozorth (D. Van Nostrand Co., Inc., 1951).

Although the ferrite catalysts can be broadly defined as containing crystalline structures of iron, oxygen and the second metallic component or components, certain types of catalysts are preferred. Valuable catalysts have been produced which contain iron, oxygen and at least one element selected from the manganese group or groups HA, HB or VIII of the periodic table such as magnesium, manganese, as the main active component in the catalyst surface exposed to the reaction gases. Calcium, cadmium, cobalt, zinc, nickel, barium, strontium and their mixtures. Preferred catalysts have iron as the predominant metal in the rope of the catalyst that is exposed to the reaction gases.

A preferred class of catalysts containing two second metallic constituents are those of the basic formula Me ₃ Cr ^ ₃ Fe ₀ O. wherein a can vary within the range from about 0.1 to about 3, b can be from greater than 0 to less than 2 and c can vary from greater than 0 to less than 3. Me can be any metallic substance apart from chromium as described above, in particular a metal from groups HA, HB, III and VIII of the periodic table. In particular, metals of these groups that are desirable are Mg, Ba, La, Ni, Zn and Cd.

The preferred compositions exhibit a certain type of x-ray diagram. The preferred composition

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tongues have no sharp X-ray diffraction reflection peaks, how to get them in highly crystalline material with the same chemical composition. Instead, the ferrite compositions according to the invention show reflection peaks, which are relatively "wide. The degree of sharpness of the reflection peaks can be reduced by the reflection peak bandwidth at half Height (W h / 2) can be determined. In other words, the width of the reflection peak as it is at half distance is determined to the top of the peak is the "band width at half height". The band width at half height is determined in units of ° 2 theta. Procedures for determining the bandwidths are given in Chapter 9 of Klug and Alexander, X-ray diffraction, John Wiley and Son, New York, 1954. The band widths observed at half the height of the preferred according to the invention Compositions are at least 0.16 ° 2 theta and generally at least 0.20 ° 2 theta. Powder diffraction images can, for example, with a Norelco diffraction unit with constant potential of the Art No. 12215/0 can be carried out with a goniometer Art No. 42273/0 with a wide range, a cobalt tube Type No. 32119 »a proportional counter type No. 57250/1 is equipped, all with a Norelco circuit panel type No. 12206/53 are connected. The Cobalt-K alpha radiation is delivered by putting the tube at operates at a constant potential of 30 kV and a current of 10 mA. To remove K beta radiation, will an iron filter used. The voltage of the detector is 1660 V and the height of the pulse analyzer will be like this set so that it only accepts pulses with amplitudes between 10 and 30 V. Have the column that will be used a divergence of 1 ° and receive 0.015 cm (0.006 inches) and a spread of 1 °. The inscription on the registration strips for the identification is done with a scanning or. Running speed of 1/4 ° / min, a time constant of 4 seconds and a full scale at 1o 'count

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gen / sec. "PUr IC alpha doublet or a" broadening the There are no bandwidths due to the instruments Corrections made. For example, excellent compositions have been made that cover bandwidths at half height of at least 0.22 or 0.23 ° 2 theta. The particular reflection peak used to determine the bandwidth at half height is the Reflection peak showing a Miller (hkl) index of 220 owns; (cf. chapter by Klug and Alexander, ibid). This relationship between the activity of the composition and the bandwidth is not intended to be a limitation on the present invention.

Suitable preferred ferrites according to the invention are zinc ferrites with X-ray diffraction peaks within d-spacing Ü3Yi of 4.83 to 4.89, 2.95 to 3.01, 2.51 to 2.57, 2.40 to 2.46, 2, 08 to 2.14, 1.69 to 1.75, 1.59 to 1.65, and 1.46 to 1.52, with the peak of greatest intensity between 2.95 to 3.01; Manganese ferrites with peaks with d-spacings within or by 4.87 to 4.93, 2.97 to 3.03, 2.50 to 2.58, 2.09 to 2.15, 1.70 to 1.76, 1.61 to 1.67 and 1.47 to 1.53 (with other peaks), with the peak with the highest intensity being between 2.52 to 2.58; Magnesium ferrites with peaks between 4.80 to 4.86, 2.93 to 2.99, 2.49 to 2.55, 2.06 to 2.12, 1.68 to 1.73, 1.58 to 1, 63 and 1.45 to 1.50, with the peak with the highest intensity between 2.49 and 2.55, and nickel ferrites with peaks within the d-spacings of 4.79 to 4.85, 2.92 to 2 , 98, 2.48 to 2.54, 2.05 to 2.11, 1.57 to 1.63 and 1.44 to 1.49, with the peak with the highest intensity from 2.48 to 2.54 lies. The preferred manganese ferrites are those in which the Mn is predominantly in a valence of plus 2.

The formation of ferrite can be achieved by reacting an active iron compound with an active connection of the desired

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Metal can be achieved. When the connection is active, a Compound understood, which is reactive under the reaction conditions and forms ferrite. Output connections from Iron or the other metal can be nitrates, hydroxides, hydrates, oxalates, carbonates, acetates, formates, halides, Be oxides, etc. The starting compounds are suitably oxides or compounds that are formed during formation decompose of ferrite to oxides such as organic or inorganic salts or hydroxides. For example, manganese carbonate can be reacted with iron oxide hydrates to form manganese ferrite.

The catalysts may contain an excess of iron over the amount stoichiometrically required to form ferrite. For example, in a ferrite of the type MeFe ₂ O ,, the stoichiometric amount of iron would be 2 atoms per atom of Me. The iron (calculated as Fe-O-) may be present in an amount at least about 10 in excess of the stoichiometric amount, and preferably it can be present in an amount of at least $ 14 in excess. Suitable iron ranges are 10 to 200? » Excess. Similarly, the catalysts may contain an excess of metal in excess of the stoichiometrically required amount.

The metal ferrite catalysts that have been produced by the process of the invention can produce higher levels of iron Have metal proportions than was previously possible. This makes lower inlet temperatures and lower ones Operating temperatures with dei * dehydration possible, with the catalysts are used. Catalysts made by known methods with high ratios from iron to metal show a rapid diminishing effect over time when used in dehydration, i.e. a loss of selectivity occurs very quickly in use.

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Various processes have been used to prepare dehydrogenation catalysts .. Although the catalyst only Can contain a single component such as iron oxide, it has been found that cocatalysts over individual Ingredients have advantages such as magnesium iron oxide. As already stated, are often metallic and non- * metallic activators, initiators, stabilizers, etc. are desired. These catalysts were made by one produced a precipitate, dry or wet wedged or mixed, a precipitate from one of the Ingredients made in the presence of the other or by adding one or more of the solid ingredients aqueous or non-aqueous solutions of salts of the to- ·; additional components coprecipitated or impregnated.

For example, a method which is previously used for the preparation of a lead molybdate / cobalt tungstate ^r had the fact that a soluble lead salt and a soluble molybdenum salt mixed. The lead molybdate is free gewaselien ~ J of electrolytes and slurried with an aqueous solution of a soluble cobalt salt, and this is precipitated as Wolfraniat by a lösli- "mixed t chen tfolframsalz. The resulting precipitate"'."Is washed free of electrolytes, dried and calcined *>'-. Metallferritoxydationsdehydrierungskatalysatoren, beispiels- ^ as magnesium ferrite, were prepared by ma-" gnesiuiüQxydpellets nitrate with a solution of iron (lII)% treated, dried and calcined. Iron (III) ^ oxyd- t "catalyst per se is often formed by precipitation, ie ι from a solution of a soluble iron salt, PECL, / is by adding a base NaOH Fe (OH), in the form of a \?

gelatinous precipitate precipitates, which is then dehydrated.

The known processes for the preparation of dehydrogenation catalysts can be roughly divided into two categories

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(1) precipitation including co-precipitation "resp. Coprecipitation, (2) physical mixing including dry and wet mixing and settling from one component of a solution to a second component. Catalysts that are commercially available, are made according to both general methods. However, it has been observed that catalysts according to the one or the other of the two categories had been produced, had more or less inner weakness or only slight Intrinsinc weakness. It is an object of the present invention to remedy this disadvantage overcome.

It has been found that catalysts made according to Category (1) above are generally poor in physical properties Show resilience. Care must be taken in handling such catalysts, and in general they must be used in beds because the speed at which they are worn away by friction or their rate of wear, their economic use in fluidized or moving bed systems excludes. In catalyst systems with many components, however, such catalysts have the advantage that a close contact of the components takes place. The catalysts produced according to the method of category (2) may have the disadvantages as described above, although generally a component or carrier is chosen which has physical strength ". However, their main disadvantage is that they are non-homogeneous and in a catalyst system with many constituents will not have the same ability or type an intimate relationship such as that achieved through the precipitation process.

The present invention provides a new process for the preparation of dehydrogenation catalysts which meet the narrow

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Allowing contact that is desired, the catalysts having been prepared by a precipitation process and yet have physical strength superior to that of the precipitated catalyst.

In the case of oxidative dehydrogenation catalysts, various other advantages and improvements provided by the present invention. So you can get higher oxygen : Use hydrocarbon ratios without substantial loss of selectivity. You get so higher yields. Lower inlet temperatures and catalyst life can still be used is at similar operating conditions in comparison with catalysts made by known processes longer.

It is also possible to better control the reaction with the catalysts of the invention. the oxidative dehydrogenation reactions are exothermic, and therefore one must use devices to control the temperature. Two special devices are heat exchange " heat removal shear or a diluent such as steam in the feed stream. In any case you can with carry out better control of the catalyst according to the invention. It has been found that the adiabatic Method the amount of steam used as a diluent can be reduced compared to that commonly used. This makes substantial savings and enables the process to be carried out becomes more profitable.

The present invention is a process for the preparation of a catalyst for use in the Dehydration, which consists in treating a solution of a soluble metal component with a precipitating agent, whereby the insoluble metal component precipitates

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is and wherein the essential feature of the invention is that at the same time with the soluble metal component a high molecular weight polyvalent organic compound is present. The term "metal component" such as as used herein means a simple metal connection or a mixture of metal compounds which have the same or different anions and / or cations.

How the polyvalent material works is not perfect known. Some polyvalent compounds can be with metals Form complexes. However, this does not appear to be essential to the present invention. The high molecular weight of the polyvalent material gives the solution polymer properties in terms of viscosity and the Surface tension. The term "polyvalent material" is intended to encompass a material that has at least two, and preferably three or more hydroxyl groups or groups that yield hydroxyl groups under the reaction conditions, contains. The term "high molecular weight" as used herein means a material having a Molecular weight of at least about 3000 (number average molecular weight) or more. The term "soluble" is used to indicate that the polyvalent material is sufficiently soluble to make the improved catalyst admit. It is generally believed that the precipitation medium is aqueous in nature, but other solvents can also be used can be used, the use of other solvents also falling within the scope of the present invention falls.

The molecular weight of the soluble polyvalent organic compounds is not critical, but it should be noted that compounds with molecular weights less than about 3000 are not perfect in forming the gel show a satisfactory result. 'It is preferred that the molecular weight is at least 4000, the

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upper limit determined by solubility considerations and also by the viscosity of the precipitation medium will. Since the precipitation agent must contact the metal ions, the viscosity of the precipitation medium must not increase be great. In general, soluble polyvalent materials, which can be mixed with the metal ions and the precipitating agent, have no molecular weights, that are greater than 400,000.

The polyhydric organic compounds that are contemplated include polyhydric alcohols including polyester like those derived from polybasic acids like adipic acid, succinic acid, sebacic acid, Azelaic acid, and phthalic acid, polyols such as pentaerythritol, xylitol and sorbitol; Polyethers like the condensation products of ethylene oxide, propylene oxide and their mixtures with polyols such as glycerine, pentaerythritol, xylitol, sorbitol and Polysaccharides and hydrolyzed polymers such as polyvinyl acetate to polyvinyl alcohol. The polyester and polyether are well known and used industrially in the manufacture of polyurethane films and foams.

The term "polysaccharide" as used herein describes a polymer that has more than two sugar units. Of course, the requirements for molecular weight would Exclude simple sugars, disaccharides, trisaccharides, etc., but some would be octa- and nonasaccharides locked in. A particularly preferred class of polyvalent compounds are polysaccharides, which have a molecular weight of at least 3000. Includes polysaccharides, the repeating units of contain simple monosaccharides (homoglycans) or mixtures of monosaccharide units (heteroglycans), for example L-pructose, xylan, D-xylose (mono) and tragacanth, D-xylose and D-galacturonic acid (hetero). The polysaccharides substituents such as amino sugar units, pentose

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sugar units, uronic acid sugar units, sugar groups, which contain ethers, among other things. The polysaccharides can be linear or branched, although branched polysaccharides, which are a preferred class, have better solubility and are therefore less likely to decompose or disintegrate into the individual components as the linear polysaccharides. The type of glycosidic bond does not appear to be critical, although 1-4 and 1-6 bonds are generally used because they are easily are accessible.

Some examples of valuable polysaccharides are Xylan, Aiüylopectine, Amylose, E'ructane, Fucan, Florida starch (floridean starch), glycogens, starches, levans (levans), dextrans and gums and slimes such as karobe (carob), tragacanth, carob (locust bean), guarana (guaran), akajou (cashew), lemons, Indian tragacanth (karaya), anogeissus slime, latifolia (ghatti), opuntia (cholla), guin-mix glue (arabic) and spilling (damson).

A preferred group of polysaccharides is selected from the group that contains potato starch, corn starch, l'apioca starch, maranta starch, gum arabic, gum tragacanth and dextran.

The high molecular weight organic polyvalent compound is typically in the metal ion solution Ranges from about 0.1 to 11 percent by weight based on the weight of the metal in the metal component, or more commonly in an amount of 1 to 4 wt .- $ calculated on the weight of the metal in the metal component.

Suitable metal salts are known essentially from all metals. The following soluble metal compounds are intended as examples of the metal components of the present invention

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Invention are mentioned: titanium trichloride, vanadium iodide, Chromium (III) nitrate, manganese (II) titanate, iron (III) nitrate, Cobalt (II) acetate, nickel nitrate, copper nitrate, niobium potassium fluoride, molybdenum dioxide dichloride, ruthenium tetrachloride, Rhodium dioxide, palladium chloride, tin (ll) chloride, antimony trichloride, tungsten dioxide dichloride, rhenium trichloride, Osmium trichloride, iridium tribromide, platinum tetrachloride, gold chloride, mercury (ll) nitrate, thallium acetate, lead fluorosilicate, Bismuth dioxide, polonium tetrachloride, magnesium selenate, aluminum bromate, calcium chlorate, scandium chloride, Zinc sulfate, strontium tetrasulfide, cadmium sulfate, barium trisulfide, beryllium bromide, lanthanum heptahydrate chloride, Cesium carbonate, germanium tetrafluoride, europium iodide, Gallium nitrate, selenium oxide, indium trichloride, etc.

In addition to the compounds indicated, less soluble compounds can be used in conjunction with other materials and processes in which their solubility is increased. For example, many insoluble compounds, such as Pe ₂ O and MgO, are soluble in hot concentrated acids. The addition of a cooled solution thereof to an alkaline solution causes the insoluble hydroxide to precipitate. Such methods and techniques are well known in the art and their use in the method of the invention is encompassed by the present invention.

The precipitating agent is any compound containing an ion that will react with the metal ion portion or portions of the catalyst to form an insoluble compound. In a large number of cases, an alkaline material such as sodium hydroxide, ammonium hydroxide, potassium hydroxide or the like provides insoluble hydroxides, e.g. Pe (OH) ₅ , Cr (OH) ₅ , Ni (OH) ₅ . Some examples of insoluble compounds made from soluble compounds are lead molybdate from lead nitrate and

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Sodium molybdate, aluminum molybdate from aluminum nitrate and Sodium tungstate, cobalt tungstate from cobalt nitrate and Sodium tungstate, etc.

The preparation of the catalysts is generally carried out at atmospheric pressure, although pressures above or below atmospheric, for example 0.5 to 50 atmospheres, can be used if conditions permit. The duration of the catalyst precipitation is generally relatively low and is about room temperature (about 25 C). Temperatures lower than room temperature can be used so long as the reactants are sufficiently soluble. In general, temperatures which are lower than 20 ^° C. are not used. Higher temperatures can be used to improve the solubility of the reactants, but in general there is no need to use temperatures in excess of 100 ^° C. At higher temperatures, ie at 30 to 50 ^° C. or higher, the viscosity effect which is brought about by the polyvalent compound with a high molecular weight is reduced.

The solutions containing the metal ion and the precipitating agent can be contacted in any known manner previously used for precipitation will. The two solutions can be mixed with little or vigorous stirring, depending on the desired particle size, are mixed together. The solution containing the metal ions can conveniently be converted into a solution of the precipitating agent be sprayed in the form of small droplets or a steady stream. Deliver the droplets Catalyst beads and the stream provides a catalyst of a cylindrical type. It has been found that the invention Catalysts produced in oxidative dehydrogenation have excellent reactivity and superior properties Possess strength. The catalysts of the invention

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are for both stationary and moving beds how to use fluidized beds.

In the preparation of the catalysts, the polyvalent organic high molecular weight compound becomes the solution given the metal ions. In general, the ionic Metal solution made by heating. Before the polyvalent compound is added, it is cooled, im generally to 100 ° C or less, preferably to 50 ° C Or less.

The precipitate that is obtained is gelatinous Material that can be easily filtered. Previously it was very difficult to process the precipitates received, because they had the inclination to look at the filter devices to fix. The filtrate obtained is washed and dried.

The catalyst thus obtained can be used without further treatment used, jedoci; one observes greater activity and selectivity, if the catalysts by heating at elevated temperatures, for example at 400 to 1100 C, in a controlled atmosphere, for example air, nitrogen, helium, or a reducing atmosphere such as hydrogen, Carbon monoxide and others activated v / ground.

Metal ferrites can be obtained by allowing the reaction to form the ferrites at relatively low temperatures is carried out, i.e. at temperatures which are lower than the very high temperatures which are used to form Gerriten used, which are manufactured for semiconductor application. The very close relationship of the metal ferrite reactants, used in the coprecipitation of the present invention facilitate this Implementation. In general, the temperatures in the reaction to form metal ferrite are lower than

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130O ⁰ C and preferably less than 115O ⁰ C. When the metal ferrite catalyst is formed, the "reaction time" at an elevated temperature can be from 5 minutes to 4 hours. The catalytic activity of the metal ferrites can be improved if the catalyst is reduced. The reduction can be carried out before the first dehydrogenation or after the catalyst has been used The reduction can be carried out with any effective reducing gas capable of reducing iron to a low valence, such as hydrogen, carbon monoxide or hydrocarbons can be from 200 to 900 ^° C. or more.

The preparation of the catalysts is often described in the literature. However, professionals often have difficulties to reproduce a particular catalyst. This disadvantage often occurs particularly in the industrial production of catalysts. The gel precipitation method of the invention has intangible but extremely valuable value as it is an easy-to-use manufacturing process creates for catalysts, the catalysts produced have uniform properties.

The catalysts according to the invention can be used for dehydrogenation can be used by a wide variety of organic compounds. Such connections are commonly

2 to 20 carbon atoms, at least one H H

-CC group and have a boiling point below about 350 ⁰ C, and they can contain other elements in addition to carbon and hydrogen such as oxygen, halogens, nitrogen and sulfur. Preferred compounds have 2 to 12 carbon atoms, and particularly preferred are compounds having 3 to 6 or 8 carbon atoms.

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Among the types of organic compounds which can be dehydrogenated by the process according to the invention, nitriles, amines, alkylhalogen compounds, ethers, esters, aldehydes, ketones, alcohols, acids, alkyl aromatic compounds, alkyl heterocyclic compounds, cycloalkanes, alkanes, alkenes, among others, are examples of Dehydrations include propionitrile to acrylonitrile, propionaldehyde to acrolein, ethyl chloride to vinyl chloride, methyl isobutyrate to methyl methacrylate, 2- or 3-chlorobutene-1 or 2,3-dichlorobutane to chloroprene, ethylpyridine to vinylpyridine, ethylbenzene to styrene, isopropylbenzene to Ethylchlorhexane to styrene, cyclohexane to benzene, ethane to ethylene to acetylene, propane to propylene or methylacetylene, allene or benzene, isobutane to isobutylene, η-butane to butene and 1,3-butadiene, η-butene to 1,3-butadiene and Vinylacetylene, methylbutene to isoprene, cyclopentane to cyclopentene and cyclopentadiene-1,3 »n-octane to ethylbenzene and o-xylene, monomethylheptane to xyl oils, ethyl acetate to vinyl acetate, 2,4,4-irimethylpentane to xylenes, etc. The invention is also valuable for the formation of new carbon-carbon bonds by removing hydrogen atoms as well as for the formation of a carboxylic compound from two aliphatic carbons. hydrogen compounds or to form a dicyclic compound from a monocyclic compound containing an acyclic group such as the conversion of propene to diallyl. As examples which can be dehydrated by the novel glazing according to the invention, are mentioned; jttbyltoltjiol, Alkylchlorbenzola, Äthylnaphthalin, Isobutyroniiril, Propylchlorid, Ieobutylchlorid, Xthylfluorid, Äthylbromid, n-Pentyliodid, Äthyldichlorid, 1,3-dichlorobutane, 1,4-dichlorobutane, among others, methyl-alcohol-ketone, methyl-butyl-ketone, methyl-butyl-ketone, methyl-methyl-ketone, diethyl-dichlorobutane, methyl-butyl-methyl-ketone, methyl-butyl-methyl-ketone, diethyl-methyl-ketone, propylchloride, propylchloride, ieobutylchloride, propylchloride

109835/1646

Suitable dehydration reactions are as follows: acyclic compounds with 4 to 5 non-quaternary neighboring Carbon atoms to the corresponding olefins, diolefins or acetylenes that have the same number of carbon atoms own; aliphatic hydrocarbons with 6 to 16 carbon atoms and at least one quaternary Carbon atom to aromatic compounds such as 2,4,4-trimethylpentene-1 to a mixture of xylenes; acyclic compounds with 6 to 16 carbon atoms and no quaternary carbon atoms to aromatic Compounds such as n-hexenes to benzene; Cycloparaffins and Cycloolefins with 5 to 8 carbon atoms to the corresponding olefin, diolefin or to the corresponding aromatic compound, for example cyclohexane to cyclohexene or cyelohexadiene or benzene; aromatic Compounds of 8 to 12 carbon atoms including one or two alkyl side chains of 2 to 3 carbon atoms to the corresponding aromatic compound with unsaturated side chains such as ethylbenzene to styrene.

The preferred compounds which are dehydrogenated are hydrocarbons, a particularly preferred class containing acyclic, non-quaternary hydrocarbons having 4 to 5 adjacent carbon atoms or ethylbenzene, and the preferred products are n-butene-1 or 2 » 1,3-butadiene-vinyl acetylene, 2-methyl-t-butene, 3-methyl-1-butene, 3-methyl-2-butene, isoprene, styrene or mixtures thereof. Particularly preferred as loading material are n-butene-t or Z and methylbutene * and dertn misöttn-'gen such as hydrocarbon mixtures which contain these compounds to at least 50 mol- #.

The dehydrogenation reaction can be at atmospheric pressure, superatmospheric pressure, or subatmospheric pressure Printing can be carried out. The total pressure of the system is generally around or above atmospheric pressure, whether

109835/1646

subatmospheric pressure can also be used. In general, the total pressure is between about 0.28 atmospheres (4 psia) and about T ₁ O? or 8.8 atmospheres (100 or 125 psia). Preferably the total pressure is less than about 5.3 atmospheric pressure (75 psia) and excellent results are obtained at about atmospheric pressure.

The organic compound that is to be dehydrated is contacted with oxygen, so that the oxygen can Compound oxidatively dehydrated. Oxygen can be in the Reactor as pure oxygen, as air, as oxygen-enriched air, as oxygen mixed with Diluents, etc. are introduced. The oxygen can also be added to the dehydrogenation zone in incremental form be added. Although provisions on the reaction mechanism are difficult, the oxidative dehydrogenation process of the present invention is a reaction in which the main mechanism is the reaction of oxygen with the hydrogen released from the hydrocarbon will is.

The amount of oxygen used can depend on the results desired, such as conversion, selectivity and the number of hydrogen atoms to be removed. To dehydrate butane to butene, less oxygen is required than if the reaction to butadiene continues. In general, oxygen (including all sources, ie the air in the reactor) in the dehydrogenation zone in an amount of about 0.2 to 1.5, preferably 0.3 to 1.2 moles / mole of H ₂ from the organic Compound is released, introduced. In general, the moles of oxygen added will range from 0.2 to 2.0 moles per mole of organic compound to be dehydrogenated and for most

109835 / 16A6

Dehydrations in the range of 0.25 "to 1.5 moles of oxygen per mole of organic compound. One of the observed advantages is that the catalysts of the invention higher oxygen to hydrocarbon ratios compared with the catalysts prepared in a known manner allow. High oxygen: hydrocarbon ratios generally provide higher conversions with a corresponding decrease in selectivity. However, the catalysts of the invention show do not allow a rapid decrease in selectivity as analogous, conventionally prepared catalysts and allow thus yields which are higher than could previously be obtained.

Often the reaction mixture contains steam or a diluent such as nitrogen, the amount generally ranging between about 2 and 40 moles of steam per mole of organic compound to be dehydrated. Preferably the steam is in an amount from about 3 to 35 moles / mole of organic compound to be dehydrated, and excellent Results are obtained in the range of about 5 to about 30 moles of steam / mole of organic compound, that is supposed to be dehydrated. The punctures of the steam are multiple, and the steam does not only act as a diluent. The diluents can generally be used in the same amounts as given for the steam have been used. These gases also serve to reduce the partial pressure of the organic compound Reduce.

The temperature for the dehydrogenation reaction will generally be at least about 25O ⁰ C, wherein it can also be higher than about 300 ⁰ C or 375 ⁰ C, and the maximum temperature in the reactor may be about

109835/16 46

700 or 800 ⁰ C or under certain circumstances higher than about 90O ⁰ O. However, excellent results are obtained in the range from about 350 to 700 ^° C. as well as in the range from about 400 to about 675 ^° C. The temperatures are determined as the maximum temperatures in the dehydrogenation zone.

The gaseous reactants can enter the reaction chamber be introduced at many flow rates. The optimal flow velocities depend on variables such as the reaction temperature, the pressure, the particle size, etc. The desired flow rates can easily be determined by preliminary experiments will. In general, the flow rates will be in the range of about 0.10:10 liquid parts by volume of the organic compound to be dehydrogenated per part by volume of the dehydrogenation zone containing the catalyst per hour (referred to as LHSV). In general, the LHSV is between 0.15 and about 5. For the calculation, the volume of a stationary bed dehydrogenation zone containing the catalyst is the original void volume of the reactor containing the catalyst.

The following examples illustrate the invention without, however, restricting it.

example 1

This example describes the production of a Mg ferrite with a weight ratio of Fe ₂ O / MgO of 9/1 according to the process according to the invention and the use of the produced catalyst in the oxidative dehydrogenation. A mixture of Fe ₂ O ₇ and MgO in a weight ratio of 9: 1 was digested in hot .. (100 to 15O ⁰ C) concentrated HCl. The solution was cooled (about 40 to 50 ⁰ C), and 2 wt .- # potato starch, be

109835/1646

based on the weight of the metal oxides, were added with stirring. This solution sol was sprayed into concentrated aqueous ammonia (28 $ NH,). A gelatinous precipitate was formed. The precipitate was aged for 1 hour, washed with distilled water by decanting, filtered and dried ^{at 16O 0 O.} 2 wt -. ° / o 85 / öiger H ^ PO, was added to the dried powder. The mixture was tabletted (0.396 cm diameter; 5/32 "dia.) And dried again. The tableted catalyst was placed in a reaction tube for testing. The reactor was vertical and was 2.54 cm (1 inch) in diameter was made of IPS stainless steel and contained a 24> 5 cm (10 inch) catalyst bed. The reactor was purged with nitrogen and set to convert n-3utene-2 to butadiene at a rate of 1.5 (LHSV) and a steam / Hydrocarbon to molar ratio of 16: 1. Two experiments were carried out at two molar ratios of Op / hydrocarbon and the results are given below.

V 'Jm m
⁰ C ( ⁰ P) Table I. Mo1ve rhaltni s
O ₂ / HC Operating
duration,
Hours. 305-340
(582-643)
318-432
(605-810) ⁽²⁾ c / s / y
Mol- # 0.25
0.69 17th
20th 40/97/39
83/95/79

^ ' T ^ = inlet temperature T _m = maximum temperature

^K ' conversion / selectivity / yield

109835/1646

The unusual effect of this catalyst in the oxidative dehydrogenation attempt is the retention of the high selectivity while increasing the conversion at the same time. Comparable results with magnesium ferrites, which have the usual FepO ^ / MgO weight ratio of 5/1, but were prepared by the known method by slurrying Fe ₂ O. and MgO, dewatered, dried, calcined, again with 2 wt. - $> 85 $ iger Η-, ΡΟ, slurried and dried again, show a butadiene selectivity that was 7 to 10 $ absolutely lower with the same conversion values.

Examples 2 to 4

A mixture of ferric chloride hexahydrate and magnesium chloride hexahydrate in a weight ratio of 9: 1 was dissolved in a barrel at room temperature. To this mixture was added 2 wt .- $ dextran with a molecular weight of 200,000 to 300,000, based on the calcined catalyst, calculated as MgFe ^ O ,. This solution sol was sprayed into a 28% ammonia solution. A gelatinous precipitate was obtained. The precipitate was aged, washed ater, filtered with distilled V / tabletted and dried at 160 ⁰ C. The catalyst was used in the form of pellets with an outer diameter of 0.24 cm (3/32 "0.D.). The same apparatus as in Example 1 was used, the pellets being a stationary bed 25, The catalyst was activated by heating. Butene-2 was oxidatively dehydrogenated to butadiene in each run. The run activation conditions and results are given in Table II. The feed ratio for each run was 1.5 LHSV .

109835/1646

Table II

In-production
game

O ₂ / KW

D / KW

Weight Yerh 'C ( ⁰ F) ⁰ C ( ⁰ F)

Gel, precipitated
from the chloride salts, calcined
at 616 ⁰ C (IHO ⁰ P)

3 in air CD Gel, precipitated CO from the chloride OO salt, calcined CO at 616 ⁰ C (IHO ⁰ F) cn in H ₂ Gel, precipitated * ^ from the chloride CD salt, calcined 'at 599 ° G (111O ° F) in air

9.0: 1

9.0: 1

9.0: 1

0.55 20 340 (645) 493 (920) 59

0.75 20 306 (585) 532 (990) 74

0.85 20 595 (313) 1020 (549) 79

0.95 20 327 (620) 545 (1015) SO

0.55 20 335 (635) 532 (990) 59 0.75 20 340 (645) 560 (1050) 70 0.85 20 340 (645) 538 (1000) 78

0.6 15 328 (623) 494 (922) 60 0.8 15 329 (624) 512 (954) 78 0.9 15 327 (621 560 (1042) 79

93 55 I. 92 68 IV) 89 70 OO 88 70 I. 93 55 91 64 89 69 94 56 91 71 90 71

T. = inlet temperature

T = maximum temperature

C / S / Y = conversion / selectivity / yield

O ₂ / HC = oxygen / hydrocarbon (molar ratio)

D / KW = steam / hydrocarbon (Mo! Ratio)

example

A time course comparison was made between a catalyst prepared in a known manner, ie a ie ^ O ^ / MgO catalyst with a weight ratio of 7: 1 and the catalyst of Example 2. The known catalyst was prepared by slurrying Fe 4 O., And MgO and forming pellets with an outer diameter of 0.24 cm (3/32 "OD) and ^{calcining at 860 °} C. (1580 ^° P) in air Conditions, ie same reactor, bed size, LHSV, steam / hydrocarbon ratio, were the same for both catalysts, with the exception of the oxygen / hydrocarbon ratio, in order to obtain comparable temperatures it was necessary for the gel-precipitated catalyst As previously indicated, one advantage of the catalysts of the present invention is the lower operating temperature; however, in order to run a time comparison test, the temperatures should be the same as the temperature has an effect on the duration of the activity of the catalyst of the experiments the inlet and maximum temperatures were varied for both catalysts and the range of changes is indicated Conditions and time trend results are given in Table III. The time trend is given as the decrease in yield per 100 hours of operation. The known catalyst was only in operation for about 340 hours because the catalyst activity decreased rapidly. The gel-precipitated catalyst was in operation for 500 hours. The feed was butene-2 which was oxidatively dehydrogenated to butadiene.

109835/1646

Table III

catalyst

LHSV (hours ~ ¹ )

/ KW

Steam / KW mol

⁰ P ( ^{0 C (}

⁰ P ( ^{0 C (}

Time trend

Decrease in butadiene

yield, moles - $ / 100 hr

CO CO CO

Gel-precipitated from 1.5 chloride salts, Pe ₂ 0, / Mg0% by weight. 90: 1, the pellets having an outer diameter of 0.24 cm (3/32 "OD), calcined at 616 ⁰ C (IHO ⁰ F) in air

mixed oxides 1.5 Fe ₂ 0, / Mg0 weight ratio 7.0: 1, the pellets having an outer diameter of 0.24 cm (3/32 "OD), calcined at 86o ⁰ C (153O ⁰ F) in air

0.85

20th

0.55

20th

310/327 552/590
(590/620) (1025/1090)

- 0.24

354/377 535/549
(670/710) (995/1020)

- 1.1

- 31 examples 6 to 8

These examples illustrate the preparation and use of a non-oxidative dehydrogenation catalyst according to the invention described.

The following procedure was used to prepare the catalyst:

(1) The active metallic components were in hot concentrated acid digested (HCl at about 100 to 150 ⁰ C).

(2) After complete digestion, the gel-forming Add means to the hot acidic metal salt solution and mix well. In the following examples 2 wt .- ^ gel-forming agent was added to the active ingredients in the form of a water-gel solution. The gelling agent used in this case was Dextran 200 with a molecular weight of 200,000 to 300,000 (Dextran 200 is available from Gallard-Schlesinger Chem. Mfg.Corp.).

(3) The acidic metal-gel mixture was added in the form of controlled drops to the precipitant, ammonium hydroxide, and a gel precipitate was formed.

(4) The gel precipitate was filtered and washed with distilled water to remove ammonia and Chlorine washed.

(5) After washing, the gel was placed in a forced air oven dried, to a particle size corresponding to a sieve with a mesh size of 0.27 mm (45 mesh size) and calcined in an open air oven at 850 to 900 ° C.

(6) The catalyst was then slurried with v / water, pelletized and dried.

109835/1646

- 52 -

The catalyst was tested in the dehydrogenation of ethylbenzene to styrene. For comparison purposes, Shell 205 dehydrogenation catalyst, which is commercially available, was used. The Shell 205 catalyst is believed to have approximately 85 Fe ₂ O ₅ and 15 $ Κ _£ 0 (wt .- ^) contains. one particular processing method .Special additives, etc., are not known. in any case all the catalysts were examined in the same manner in a micro pulse catalytic reactor..

The apparatus included a known gas chromatograph with a small, tubular, stainless steel, stationary bed reactor mounted in the carrier gas stream between the sample valve and the distribution column. Samples of the reactants were injected into the sample inlet and mixed with the carrier gas (helium) which flowed down through the 1 inch (2.54 cm) catalyst bed. The reaction products were separated directly on a type R P and Ε column (V con operated with polypropylene at 90 ^° C. and 1.41 atmospheres (20 psi)) and quantitatively analyzed using a thermal detector. The carrier gas velocity was constant at 4-6 cc / min, giving a contact time of about 0.2 seconds. The conditions and results of the various dehydrations are given in Table IV »

109835 / 1-646

- 55 -

catalyst
(Weight-5t) Tabel IV CS Y
MoI- * styrene 98 76 Bel-
game £ 80 MgPe ₂ O ₄
(Relationship
Fe ^ / MgO 4.5: 1)
51t K ₂ CO ₃ , 15pcs
CrCl ₃ ⁰ C ( ⁰ F)
Temp. Sample size
Microliter /
input 77 99 87 6th 70Jt MgFe ₂ O ₄
(Relationship
* e ₂ 0 ₃ / Mg0 4.5s1)
5 * K ₂ CO ₃ , 25 *
ZnCrO ₄ 343
(650) 3:00 88 91
88 36
74 7th Shell 205 393
(740) 3 * 00 40
83 8th game 9 460
(860)
521
(970) 3 s 00
3 j OO A mixture of ferric chloride hexahydrate and manganese hexahydrate
hrdrat in a weight ratio τοη 2s1 was in tfasi m
ier at

dissolved at zinc temperature. Dextran (WITH 200,000 to 300,000) was added until a 5% strength by weight solution was obtained “calculated on the weight of the MgFe ₂ O ₄ , (calculated) in the finished catalyst. This solution was sprayed into an aaaonia solution. A gelatine-filled bodice was obtained which was aged for 30 minutes, filtered with distilled water and whitened in a solution of H ^ FO ₄ (approx ■ lt an aperture τοη ca 2 to 3 equivalent (7 to 10 Msh) was applied and was dried at 140 ⁰ C.

109135/1646

The dried pellets were (1 ⁿ⁾ in a 2.54 cm -Vycor-Heaktor in a 13 cc bed and reduced for 1 hour at 45O ⁰ C. After the reduction, the temperature was lowered to 325 ° C and the charging of steam, lust and butene-2 was started. The molar ratios of steam: oxygen! Hydrocarbon were 22 / 0.5 / 1, LHS? was 1.0. The initial temperatures were 288 to 316 ° C (550 to 60O ⁰ F) ₁ the maximum temperature was 416 ° C (780 ° F). The C / S / Y ratio after 4 hours of operation was 56/94 / 52.6. The air was increased to 0.75 and no significant increase in temperature was observed, ie a maximum of 790 ° C. After the plant had been in operation for 4 hours and 20 minutes, the C / S / Y ratio was 76.6 / 91/69 »7.

10iS35 / 1i4

Claims (1)

- 35 claims 1. A process for preparing a catalyst for use in dehydrogenation by treating a dissolving a soluble metal component with a precipitant, Filling in an insoluble metal component, thereby g e k e η η ζ e i c h η e t that the soluble metal component together with a soluble, polyvalent high molecular weight organic compound is present. 2. The method according to claim 1, characterized in that that the insoluble metal component is calcined. 3. The method according to claim 1, characterized in that the molecular weight of the soluble, polyvalent organic High molecular weight compound is at least about 3,000. 4. The method according to claim 3 »characterized in that the molecular weight of the polyvalent compound is between 4,000 and 400,000. 5. The method according to claim 4 »characterized in that the polyvalent compound has at least three hydroxyl groups contains in the molecule. 6. The method according to claim 4, characterized in that the polyvalent compound is a polyester or a Is polyether. 7. The method according to claim 5 »characterized in that the polyvalent compound is a polysaccharide. 8. The method according to claim 7 »characterized in that the polysaccharide is branched. .- 36 - 9. The method according to claim 8, characterized in that the polysaccharide 1-4, 1-6 or mixed glycoside bonds contains. 10. The method according to claim 8, characterized in that the polysaccharide is selected from the group which contains potato starch, corn starch, tapioca starch, maranta starch, gum arabic, gum ragant and dextran. 11. The method according to claim 1, characterized in that 0.1 to 11 parts by weight of the polyvalent compound, calculated on the weight of the metal, are used. 12. The method according to claim 11, characterized in that 0.1 to 4 wt .- $ used of the polyvalent compound will. 13. The method according to claim 1, characterized in that that the solution of the soluble metal component and the precipitant contact one another with stirring will. 14. The method according to claim 1, characterized in that the solution of the soluble metal component in the Precipitant is sprayed. 15. The method according to claim 1, characterized in that the soluble metal component is at least one metal with at least two oxidation stages from groups IVB, VB, VIB, VIIB, VIII, IB, IVA, VA or VIA of the periodic System of elements contains. 16. The method according to claim 15 »characterized in that that the soluble metal component contains at least one metal selected from the following group: Ti, V, Cr, Mn, Fe, Go, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Sn, Sb, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi and Po. 109835/1 6 Λ 6 -17 «Method according to claim 15, characterized in that that the soluble metal component is at least one metal with a single oxidation stage from groups IA, HA, IHB, IVB, VB, VIIB, IB, HB, IHA or IVA des Contains Periodic Table of the Elements. 18. The method according to claim 16, characterized in that the soluble metal component at least one Contains metal selected from the following group: Mg, Al, Ca, Sc, Zn, Sr, Cd and Ba. 19. Process for the preparation of an oxidative dehydrogenation catalyst according to claim 1, characterized in that the soluble metal component iron and contains at least one other metal, provided that the insoluble metal component is an oxide, a mixture of oxides or compounds which are precursors of oxides. 20. The method according to claim 19, characterized in that the other metal is selected from the following Group: Mg, Zn, Ni, Co, Mn, Cu, Cd, Ba, Sr, Al, Cr, Ti, V, Mo, W, Na, Li, K, Sn, Pb, Sb, Bi, Ga, Ce , La, Th, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and their mixtures. 21. The method according to claim 20, characterized in that the other metal is selected from the group it contains Mg, Ca, Sr, Ba, Mn, Cr, Co, Ni, Zn, Cd and their mixtures. 22. The method according to claim 21, characterized in that the other metal is Mg or Mn. 23. The method according to claim 22, characterized in that that the solution of a soluble metal component is iron 1 O s> '-: -; Π / 1 Γ. Λ β oxide and magnesium oxide in hydrochloric acid and
that the precipitating agent is an alkaline solution and the insoluble compound is iron hydroxide and magnesium hydroxide. 24. The method according to claim 19 »characterized in that the polyvalent organic compound with high Molecular weight is a polysaccharide. 25. The method according to claim 19, characterized in that the polyvalent organic soluble compound
high molecular weight is a polyester or a polyether. 26. The method according to claim 20, characterized in that the soluble, polyvalent organic compound having a high molecular weight is a polysaccharide with a
Molecular weight of at least 3000. 27. The method according to claim 26, characterized in that the polysaccharide has a molecular weight in the range from about 4,000 to 40,000. 28. The method according to claim 26, characterized in that the polysaccharide is branched. 29. The method according to claim 28, characterized in that the polysaccharide 1-4, 1-6 or mixed
Contains glycosidic bonds. 30. The method according to claim 28, characterized in that the polysaccharide is selected from the group which contains potato starch, corn starch, tapioca starch,
Maranta starch, gum tragacanth and dextran. 31. The method according to claim 20, characterized in that 0 μ Γ? ö iw 1 ^: o '■ B net that one 0.1 to 11 wt. ^ polyvalent compound, ■ calculated on the metal weight, used. 52. The method according to claim 31, characterized in that 0.1 to 4 wt .- $ of the polyvalent compound used. 33. The method according to claim 23, characterized in that the organic soluble polyvalent compound high molecular weight is a polysaccharide. 34. The method according to claim 33, characterized in that the polysaccharide potato starch \ Lst. 35. The method according to claim 34, characterized in that the solution of the soluble metal component in the precipitant is sprayed. 36. A dehydrogenation catalyst prepared according to claim 1. 37. A dehydrogenation catalyst prepared according to claim 2. 38. A dehydrogenation catalyst prepared according to claim 4. 39. A dehydrogenation catalyst prepared according to claim 6. 40. A dehydrogenation catalyst prepared according to claim 7 » 41. A dehydrogenation catalyst prepared according to claim 8. 109835/1646 42. A dehydrogenation catalyst prepared according to claim 15. 43. One-dehydrogenation catalyst prepared according to claim 16. 44. A dehydrogenation catalyst, prepared according to claim 17 « 45. A dehydrogenation catalyst prepared according to claim 18. 46. A dehydrogenation catalyst prepared according to claim 19. 47. A dehydrogenation catalyst prepared according to claim 20. 48. A dehydrogenation catalyst prepared according to claim 21. 49. A dehydrogenation catalyst prepared according to claim 22. 50. A dehydrogenation catalyst prepared according to claim 23. 51. A dehydrogenation catalyst prepared according to claim 26. 52. A dehydrogenation catalyst prepared according to claim 30. 53. A dehydrogenation catalyst prepared according to claim 34. 109835/1646 54. Process for the oxidative dehydrogenation of an organic Compound containing at least two adjacent hydrogen atoms and the carbon atoms in the presence of a catalyst, characterized in that the catalyst according to Claim 46 is used. ' 55. Process for the oxidative dehydrogenation of an organic compound containing at least two adjacent hydrogen atoms and contains the carbon atoms, in an- Sheit of a catalyst, characterized in that the catalyst according to claim 47 is used. 56. A process for the oxidative dehydrogenation of an organic compound which contains at least two adjacent hydrogen atoms and the carbon atoms, in the presence of a catalyst, characterized in that
the catalyst according to claim 48 is used. 57. A process for the oxidative dehydrogenation of an organic compound which contains at least two adjacent hydrogen atoms and the carbon atoms, in the presence of a catalyst, characterized in that
the catalyst according to claim 49 is used. 58. A process for the oxidative dehydrogenation of an organic compound which contains at least two adjacent hydrogen atoms and the carbon atoms, in the presence of a catalyst, characterized in that
the catalyst according to claim 50 is used. 59 · Process for the oxidative dehydrogenation of an organic compound which contains at least two adjacent hydrogen atoms and the carbon atoms, in the presence of a catalyst, characterized in that
the catalyst according to claim 51 is used. 109835/1646 60. A process for the oxidative dehydrogenation of an organic compound which contains at least two adjacent hydrogen atoms and the carbon atoms, in the presence of a catalyst, characterized in that
the catalyst according to claim 52 is used. 61. A process for the oxidative dehydrogenation of an organic compound which contains at least two adjacent hydrogen atoms and the carbon atoms, in the presence of a catalyst, characterized in that
the catalyst according to claim 53 is used. 62. Process for the dehydrogenation of an organic compound containing at least two adjacent hydrogen atoms and which contains carbon atoms, characterized in that that the catalyst according to claim 36 is used. 63 Process for the dehydrogenation of an organic compound, which contains at least two adjacent hydrogen atoms and the carbon atoms, characterized in that, that the catalyst according to claim 38 is used. 64. Process for the dehydrogenation of an organic compound containing at least two adjacent hydrogen atoms and which contains carbon atoms, characterized in that that the catalyst according to claim 40 is used. 65. The method according to claim 54, characterized in that the organic compounds are hydrocarbons are. 66. The method according to claim 58, · characterized in that the organic compounds are hydrocarbons are. 109 8 35/1646 67. Process for the production of a metal ferrite as oxidative dehydrogenation catalyst, characterized in that it contains iron and at least one other metal according to Claim 1 contains. 68. The method according to claim 67, characterized in that the other metal is selected from the group which contains Mg, Ca, Ba, Mn, Cr, Co, Ni, Zn, Cd and their mixtures, 69. The method according to claim 68, characterized in that a magnesium ferrite is produced. 70. The method according to claim 68, characterized in that that a manganese ferrite is produced. 71. The method according to claim 69, characterized in that the polyvalent organic compound is a polysaccharide is. 72. The method according to claim 70, characterized in that that the polyvalent organic compound is a polysaccharide. 73. Metal ferrite catalyst prepared according to claim 74. Magnesium ferrite catalyst, prepared according to Claim 69. 75. Manganese ferrite catalyst, produced according to claim 70. 76. Process for the oxidative dehydrogenation of organic compounds containing at least two adjacent hydrogen containing atoms and carbon atoms, characterized that a catalyst according to claim is used « 109835/1646 77. Process for the oxidative dehydrogenation of hydrocarbons containing at least two adjacent hydrogen atoms and carbon atoms, characterized in that, that a catalyst according to claim 69 is used. 78. The method according to claim 77, characterized in that the hydrocarbons are n-butenes. 79. Process for the oxidative dehydrogenation of hydrocarbons, which contain at least two "adjacent hydrogens and the carbon atoms, characterized in that that a catalyst according to claim 70 is used. 80. The method according to claim 79, characterized in that the hydrocarbons are n-butenes. 109835/1646