NL7908202A - PROCESS FOR CATALYTIC HYDRATING OLEFINS - Google Patents

Description

* 70 8595

Process for the catalytic hydration of olefins.

The invention relates to processes for the hydration of olefins and more particularly to such processes using metallic oxide catalysts. The use of metal oxide catalysts for the hydration of olefins to the corresponding alkanols is known. U.S. Patents 1,873,536 and 1,907,317 disclose olefin hydration catalysts containing one or more oxides of aluminum, thorium, titanium, tungsten, and chromium.

Set US Patent 1,882,717 describes the use of oxides of antimony, manganese, tungsten, zinc and / or tin oxides as promoters of metal phosphate ethylene hydration catalysts.

U.S. Patent 1,977,633 indicates that it is known to use compounds of gold, iron, chromium, vanadium, tungsten, mc-15 lybdenum, and manganese for the olefin hydration. U.S. Patent 2,162,913 describes an alkylene hydration catalyst which is an inorganic, core element complex such as silicon or boron surrounded by a coordinated group of another metal oxide or oxides such as tungsten oxides, molybdenum, vanadium, chromium and tellurium. It

U.S. Patent 2,769,347 discloses a binary metal oxide olefin hydrate catalyst in which ferric oxide is thoroughly mixed with titania. U.S. Patent 3,076,036 describes a catalyst composition for hydrating olefins with 3-5 carbon atoms, which contains molybdenum oxide in combination with silica and an oxide of at least one metal of groups Illb and 17a of the Periodic System, such as alumina , hafnia, zirconia, titania and thoria. With the exception of U.S. Pat. No. 2,769,347, none of the references disclose the use of a binary or ternary metal oxide-olefin hydration catalyst composition, i.e. z. a catalytic converter 7908202 2 incorporating the metal oxide components. more intimate cohesion than is attainable by mere mechanical mixing.

It has now been discovered that certain binary, ternary and other mixed metal oxides are very active as catalysts for the hydration of olefins in liquid or darap phase. The metal oxides useful as olefin hydration catalysts include reacted oxide compositions of at least one metal oxide with an electro-negativity X ^ for the metal ion greater than about 20.0 with at least another metal oxide whose electronegativity value X ^ for its metal ion is greater than about 13.0. The electronegativity value is calculated from the relationship X. = (1 + 2Z) Xq, where Z is the charge of the metal ion and X is the electro-negativity value of the o neutral metal atom assigned by Pauling (and indicated 15 in such standard works as Lange's Handbook of Chemistry, Eleventh Edition), In contrast, the binary catalogs composition of U.S. Patent 2,769.8UT combines two metal oxides, ferric oxide and titania, each of which has an electronegativity value of X .. for the metal ions. of not greater than about 1U, 0 and as such are much less active than the metal oxide hydration catalysts listed herein.

The terms "reacted oxide composition" and "reacted relationship" refer to an association of metal oxides that is close to that achievable by mechanical mixing of the oxides alone. It is hypothesized that in binary oxides, such as silica-alumina, an amorphous replacement of a metal ion with a second metal ion takes place in the oxide grid of the latter. Another hypothesis assumes that the oxide of one of the metals can become a terminal group in the milk structure of the other, coordinating its metal ion with hydroxyl and water. However, the actual mechanism by which the reacted oxide compositions are formed cannot be considered a limitation of the invention to be described.

According to a process for preparing the aforementioned metal oxide catalysts, aqueous solutions of the selected metals are formed in the form of their water-soluble salts, e.g. the halides, nitrates, phosphates, etc., are contacted with a base, such as ammonia, with associated coprecipitation of the metal oxides. The oxides are separated from the top fluid layer, dried and optionally calcined in a non-10 reducing atmosphere.

Another method ("slurry growth"} that can be used to prepare the metal oxide catalysts of the invention utilizes heating an aqueous slurry of the selected oxides while precipitating the reacted oxides together. liquid gas, as reported in Batist, et al. J. Cat. Vol. 12, biz. 60 (1968), and cation of the dried precipitated oxide in a non-reducing atmosphere.

Examples of metal oxides with an electronicity value X- for the metal ions greater than about 20 useful for the invention are summarized in Table A.

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The amounts of the individual metal oxides can be freely selected in a relatively wide range of values, it should be noted that generally the higher the X value for the selected oxides, the greater the activity of the resulting catalyst for the olefin hydration reaction. Accordingly, the preferred catalysts will contain oxides each having an X .. greater than about 20.0, for example, combinations of MoO2 and WO2 or MoO2 and Sb2 O5. or combinations of an oxide with an X ^ greater than 10 about 20.0 and an oxide with an X ^ greater than about 13.0, but less than about 20.0, the total number of metal atoms of the oxide having a higher X ^ is at least equal to the total number of metal atoms of the oxide with lower X .., e.g. a combination of MoO 2 and SbgO 2 in a molar ratio of about 2: 1. Other preferred combinations of metal oxides in addition to those illustrated in the examples include the binary oxide UOO ^ SnOgs in which the atomic ratio is within the range of about 0.3 to 0.6 and the binary oxide 02ο02 ~ 020 ^ in which the atomic ratio Mo / Y + Mo is within the range of about 0.3-0.6. If desired, the metal oxide catalysts of the invention can be applied in known manner to any of the various known or conventional carriers, such as silica, alumina, titania, thoria, hafnia, etc., and mixtures thereof.

The catalysts of the invention are useful for effecting the hydration of a wide variety of mono-, di- and polyethylenically unsaturated olefins to yield the corresponding alkanols and are particularly suitable for the hydration of lower mono- Olefins, such as ethylene, propylene and butene-1. In carrying out the hydration reaction, the olefin vapor is contacted with the catalyst either continuously or batchwise under suitable conditions of temperature and pressure in the presence of a molar excess of water relative to the olefin. The conditions of temperature and pressure may be such that the water is partly in the liquid phase or entirely in the vapor phase. Catalytic hydration can be performed under a variety of conditions. Usually, the temperature used is approximately within the range of 150-375 ° C, and preferably between about 250-325 ° C. The pressure used depends on the desired temperature and the reaction phase. Pressures in the approximate range of 17-700 bar overpressure are suitable, with an overpressure between about 35 and 350 bar being preferred. The water olefin molar ratio required in the reaction zone varies depending on the vapor phase and the mixed phase treatment. Generally, the molar ratio of water to olefin reactant will be in the range of 2: 1-5: 1, with a preference of 20: 1 - Lo: 1.

In the following examples, the general operating procedure for conducting each liquid phase ethylene hydration reaction was as follows:

A stainless steel microreactor with an internal diameter of 3 mm, an external diameter of 11 mm and an operating pressure of approx. 1000 bar was placed in a vertical position, charged with 1.0 g of binary metal oxide catalyst and 1.5 cc of water and closed. Ethylene at a pressure of 55 bar and at ambient temperature was admitted to the reactor and the reactor was shaken for 5 min before starting the heating. The reactor was then heated to 300 ° C and held at this temperature for the duration of the hydration reaction (approximately 30 min), then heating was stopped, the shaker stopped and the reactor was rapidly cooled to 25 ° C by covering it with COg powder. After the reactor was vertically placed in a container surrounded with CO 2 powder, the temperature was allowed to drop to -1 ° C, then gas was vented from the reactor via 2 cc of methanol cooled with dry ice and then by a wet test for the volume measurement. After the input of 1.0 cc (Q, 3Q g} n-propanol into the reactor, the reactor was inverted, placed in 7908202 • 10 warm water and heated to 30 ° C and then placed on a shaker and for 15 min. shaken. The reactor was then cooled to 18 ° C in wet ice, opened and its contents including the methanol wash liquor analyzed by gas-liquid chromatography on alcohol and ether.

The ethanol produced is reported as grams of alcohol per gram of catalyst per hour.

Example I

An unsupported binary oxide of iron and 10 molybdenum prepared by coprecipitation of ammonium molybdate and ferric chloride with ammonia followed by calcination of the precipitate at 100 ° C as described in U.S. Patent 3,152,997 to methanol oxidation catalysts , yielded an average of 0.12 g of ethanol based on five experiments. The recovered solid produced 0.1 µg of ethanol in a run, while the blue-colored recovered upper liquid layer gave 0.02 g of ethanol.

Example II

An unsupported binary oxide cat alys ator 20 composed of antimony and molybdenum in one. atomic ratio (Mo / Mo + Sb) = 0.5 was prepared by keeping an aqueous suspension of SbgOj and MoO ^ at 90 ° C for 5 days ("slurry growth"), then drying and calcining at 500 ° C. The catalyst gave an average of 0.1 hg of ethanol based on three runs. Another binary oxide catalyst with an atomic ratio (Sb / Mo = 1.0) was prepared by drying an aqueous suspension of Sb 2 O - in ammonium molybdate followed by calcination at 500 ° C. This catalyst produced 0.1 µg ethanol.

Example III

An unsupported binary oxide of tin and molybdenum was prepared by slurry growth as in Example II using SnO 2 and MoO 2 at an atomic ratio of Sn: Mo of 1.0. This catalyst produced 0.11 g of ethanol.

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In each of the aforementioned examples, the amount of ethanol produced ranged from not less than 1.5 to as much as four times the amount of ethanol produced by a standard catalyst, in which 18.9 wt% WO 2 on titania was reduced with hydrogen at 1 + 00 ° C for 8 hours (¥ 0 ^ reduced to ¥ ^ 01i). The standard catalyst produced only 0.036 g of ethanol as an average of 11 runs at 280 bar nominal pressure.

In the following two examples, the conduct of the liquid phase ethylene hydration reaction was modified by the ethylene admission into the reactor at about 100 bar and the internal analysis standard being ethyl acetate instead of n-propanol. The standard catalyst produced 0.20 g of ethanol under these conditions.

Example XII

The catalyst comprised reacted SbgO 2 and ¥ 0 in in a ratio of 1 + 5% 0 0:: 55% Sb 2 O 2. and was prepared as follows: 1.8 g of ammonium metawolframate [was dissolved in 5.0 ml of HgO and added to a solution of 2.0 ml of SbCl 2 (1 +, 67 g) in 10% HCl solution. Dry KH2 was added until the pH reached 3.0 to co-precipitate the oxyies.

The precipitates were aged overnight, after which the mixture was evaporated to dryness over the steam bath. The catalysts produced 0.28 g of alcohol.

Example XIII

The catalyst comprised 9% Bi ^ O ^: 91% 1 prepared as follows: 1 + 3.5 g of ammonium meta-tungstate [(UH ^ JgW ^ O ^ .OH ^ O] and 3.1 + 8 g Bi (110 ^) ^ 5 ^ 0 were placed in a 200 cc glass beaker with 100 ml distilled water Six drops of concentrated 30 · HHO 2 were added and the preparation was stirred until the solution was effected, after which the water was evaporated at 115 ° C. The solid was then reduced with flowing hydrogen at 1 + 00 ° C for 8 hours after which it was calcined at T00 ° C under helium The catalyst provided 0.30 g of alcohol.

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Claims (10)

1. A process of strange catalytic hydration of an olefin, characterized in that the catalyst contains a water-insoluble metal oxide mixture of different metal oxides in a reacted relationship, the metal ion of at least two of these metal oxides having an electronegativity value greater than 20. or wherein at least the metal ion of one of these metal oxides has an electronegativity value X ^ greater than 20 and at least the metal ion of one of said metal oxides has an electronegativity value X.1 of 13-20, where the total number of metal atoms with a higher X ^ is at least equal to the total number of metal atoms of the oxide with lower X. 2 * Process according to claim 1, characterized in that the mixed metal oxide is obtained by contacting an aqueous solution of at least two water-soluble metal salts with a base for coprecipitating the metals as their metal oxide mixture. 3. Process according to claim 1, characterized in that the metal oxide mixture is obtained by heating an aqueous suspension of at least two water-soluble metal oxides. k. . Process according to claims 2-3, characterized in that the obtained mixed metal oxide is recovered, dried and calcined in a non-reducible atmosphere. Process according to claims 1 - k, characterized in that the mixed metal oxide contains at least two metal oxides selected from McO, WC, * W. Q ^ 1, TeC2, Au0?, CrC ^ or Sb ^ CL, the metal ion thereof having an X ^ greater than 20. o. Process according to claims 1 - characterized in that the mixed metal oxide has at least one metal oxide contains, selected from MoO ^, WO ,, W ^ 0n,? e02, TeC ,, AuO ,, CrO, or Ξο, Ο, -, ^ Λ · = »^ Λ · '· <JAVL r 111 · $ whose metal ion thereof has an X ^ value greater than 20 and at least one metal oxide selected from TiOg, FegO ^, MhO ^, SnOgj Si02, Mo02, W02, VgO ^, Y0 ^ s Ta ^, RuOg, Bh ^, RhOg, ReOg, ZnOgj CrO 2, B 2, BigO 2, Sh 2 ° 3 or ZrO 2 '5 Process according to claims 1 to 11, characterized in that the metal oxide mixture MoO 2 in reacted relationship with at least a 0 × 7th selected from Sb. ^ 0 ^, FeVgO ^, BigO ^, Zr02 or Zn02. 8. Process according to claims 1-7, characterized in that * the hydration reaction proceeds in liquid phase. 9. Process according to claims 1-7, characterized in that the hydration reaction proceeds in vapor phase. 10. Process according to claims 1-9, characterized in that the olefin is ethylene, propylene or butene-1. Process according to claims 1 to 10, characterized in that the metal oxide is present on a support. A method according to claim 11, characterized in that the carrier is silica, alumina, titania, thoria or mixtures thereof. Process according to Claims 1 to 12, characterized in that each metal oxide component of the catalyst has an electro-negativity value X> greater than 20 for the metal ion. possession of it. 1 ll. Catalytic hydration catalyst of each one, characterized in that the catalyst is one. water-insoluble metal oxide mixture of different metal oxides in a reacted relationship, wherein the metal ion of at least two of the metal oxides has an electronegativity value X ^ greater than 20 or wherein the metal ion of one of the metal oxides has an electronegativity value X. greater than 20, and at least the metal ion of one of the metal oxides has an electronegativity value X ^ of 13-20, the total number of metal atoms having an X- greater than 20 being at least equal to the total number of metal atoms of the oxide having a 7908202 * lower X .. Catalyst according to claim 1, characterized in that the metal oxide mixture contains at least two metal oxides selected from MoG, WG ^, ^ - ^ 23 ^^ 35 AuO ^, Cr0 ^ or Sb ^ O-, 5 by their metal ion. an X ... possessed greater than 20 possession. 6. Catalyst according to claim 11, characterized in that the metal oxide mixture MoO4 is in reacted relationship with at least one oxide selected from SbFe, V2 ° 5, BigO2, ZrOQ or Zn0o. 7908202