CS199849B1 - Process for the preparation of tert-butanol and maleic anhydride - Google Patents

Abstract

The aim of the invention is to comprehensively petrohemdically evaluate a mixture of saturated and unsaturated hydrocarbons from cracking, especially the pyrolysis C^-fraction from the pyrolysis of gasoline and higher petroleum fractions. This is achieved by a two-stage process, where in the first stage isobutene is selectively reacted with water to form tert-butyl alcohol under the catalysis of strong alkaline ionic compounds and in the second stage the hydrocarbons are subjected to oxidation with oil to obtain maleic anhydride. The unconverted hydrocarbon mixture is recirculated or used as a high-energy fuel.

Description

According to the present invention, a mixture of saturated and non-saturated hydrocarbons of ketacevanla, in particular pyrolysis of petroleum pyrolysis and also of fractionated petroleum oils, and a simultaneous production of toroilane butanol and maleate, is evaluated.

Well-known production of terolerae butanol by dilution of elic acid (65%) and fracol pyrolyte ^ Aeineor Pi Dia potroohomloo Indu · trio, pp. 1081-1083, AkadeodLeVorlac, Bořila 0971)] » postponing elric acid and residues, if necessary, by ioh Salzio's petrochemical recovery. Said method and method is based on the isolation of isobutylene and olefin mixtures with the paraffin of Nazarov S.S. prlkl. Ohim, 33, 448 (1965)]. Also known (DAS 1 176 114) is the continuous production of tert-butanol and isobutylene. However, the lack of these processes is also due to the fact that nobody and a consideration of selectivity and the other components of the pyrolysis fraction. Salary! including the production of a hydrocarbon-based maleic anhydride of said fraction, on the one hand, e.g. raw material

Ion butadiene 00 with air and water vapor (Jap. Pat. 46-22009, 46-25736), which is or may be a valuable monomer and comonomer, or 1-butene itself with air (Jap. Pat.

45-22326, 45-21688). However, 2-butenes alone by air (v. British Pat. 1,157,117 and US Pat. 3,484,384) or pyrolysis and frakoia (P. Pat. 2,022,272,

In * Brit. pat. No. 1 291 354), in which, in turn, it does not use isobutane and n-butane for its own synthesis (isobutane o and epaTujo, and n-butane remains unchanged in miaSnoj). Finally, the catalysts can be prepared on a vanadium-phosphorus-free catalyst at an V / P atomic ratio of 0.5 to 2 and in the presence of pro-promoters (Cr, Pe, Hf, Zr, La, Ce). 420-600 ° C (U.S. Pat. No. 3,888,886). True, pyrolysis of C fr fr frakoakoiaia vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy vždy komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty fr komponenty komponentynéné komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty komponenty isobutane, butadiene is also an expensive raw material for the production of maleic anhydride. On the other hand, it is necessary to select reaction conditions such that, in addition to butadiene and n-butenes, n-butane is also a raw material for the small anhydride.

These problems in the case of the application of a mixture of saturated and non-saturated hydrocarbons and the controlled production of t-butanol and maleanoanhydride epidobium according to the invention.

According to the present invention, the epdeobic production of toro-butanol and maleate hydride from pyrolysis O-frakel, preferably pre-de-butadiene, is carried out in that the pyrolysis fraco aa introduces an appeal with water, preferably in water vapor, at a temperature of 40 to 160 ° C. preferably 50 to 120 ° C; and preferably a high-strength cathoxone, at atmospheric pressure of up to 10 MPa, preferably 0.5 MPa to 3 MPa, of the reaction product formed, substantially free of isobutane with water to tert-butaaol, preferably of alkanol and hydrocarbons. and, in addition to the co-added gas containing oxygen, preferably air or oxygen, optionally mixed with water vapor, at a temperature of 350 to 650 ° C, preferably 400 to 550 ° C, to the oxide catalyst, It isolates and unconverts a mixture of hydrocarbons

• the advantage re-circulates the task aa and at least removes the part ua incinerated.

As solvents, especially for increasing the water content and the carbohydrate content, ethers, dioxane, tetrahydrofuran may be used, but it is most suitable to apply torolar butanol which is completely ground in the water, but is not even complicated. Suited to apply * rooirlculevaný torolární butanol and water, the boat and absorbed part * energy on joho rařináoiu. In addition, especially if aa adds water alone to the reaction medium, it is advisable to add water-active substances to the water, and to emulsify the emulsifiers to make it possible for the isobutyl-naphthylic surface to be applied with water.

In the funcol anaolvokyaelin ** when the roocoa is carried out in gaseous, reap. in the parnoy phase, yeah appropriate to apply ’in addition to thick acid. various phosphorousnene catalysts, e.g. PgOg on ailikagáli, pumice, zoolitooh and the like. In the case of an appellant in the liquid phase, the most insoluble types are science insoluble.

In the case of hydratool temperatures, it is desirable to heat at 40 ° C to 16 ° C, but with increasing temperatures the selectivity of hydratool decreases rapidly, and isobutene oligomerization of olefins begins to take place. Therefore, the application of temperatures in the range of 65 to 85 ° C appeared to be the most suitable, in which sufficient reaction coefficient and high selectivity of hydratool isobutyleate and low coefficient of olefin oligomerization were found.

As the oxidation catalysts of a mixture of both saturated and non-saturated C ^-hydrocarbons to malonate hydride, account is taken, in particular, of oxygen-containing vanadium-phosphate with a propylene or at least iodine-containing element (s) of the following compounds, in particular: , Co, Mo, TI, V, & g.

An advantage of the method according to the invention is the high-temperature iodine resistance, the complicated petro-hemi-use of the pyrolysis ako fraction. The high selectivity of individual reaction steps, relatively low energy intensity * and considerable prooos flexibility. Last but not least, the fact that the degree of refinery oil may be dispensed with (e.g., by the elective hydrogenation of alkanes and propane) by isolating butadiene, except for investment savings, will reduce the losses of butadiene. Further advantages are apparent from the examples.

Example 1

A reactor filled with a strongly acidic cation exchange resin based on a sulphonated polydivinylbutyrate gland at a temperature of 70 ° C to 3 ° C is continuously fed from hydrocarbons of the pyrolysis C 1 fraction (composition: 4 µl by weight 1,3-butadiene; 21.2 µl by weight isobutene; 1 fi wt.

1-Tuta; 4.0 fi wt. OLS-2-butane; 4.8 fi wt. tran-2-butane; 12.3 fi wt. n-butane;

0.6 fi wt. isobutene; 0.5 fi wt. uhTovodlkov; 0.5 fi wt. 0 $ abXwo & tls & r and 0.8 fi wt. aoetylénlekýoh uhTovodlkov Alan) at 350 g.1y. ".. ^ * h ^and the participation of

6 ° e.lj ^ .h ¹ aqueous solution of tert. butanol o cono. 50 fi wt. The crude reaction product is sucked next to a distillation column, whereby liquid products are removed from the column.

199 849 contentsJos basically. butanol (< 93% by weight), a small amount of water and diisobutenes, and a small amount of lower alcohols which are either used directly or which lead to rectification. This gives 74 g.1 ^ _t .h ” ¹ taro. butanol.

Essentially, it discards a mixture of hydrocarbons at the top of the column containing (in # mass)

50.2 butadiene, 1.1 isobutonized with 19.2 1-butene, 5.1 ois-2-butene, 6.1 trans-2-butene,

15.6 n-Butonized with 0.8 isobutane and 2 other C8 to C8 hydrocarbons. The conversion of isobutene is thus 96%, butadiene is about 3.8%, but 1-butene and 0.2%, and 2-butenes are approximately 0.4%.

The hydrocarbon mixture at the top of the column is then mixed at atmospheric pressure with an air pressure of up to 1.4 phy vol. hydrocarbons in the mixture besides the kysllčníkový oxidation catalyst (13.9% P ₂ O ₅ 4.5% W J ₂ J 0 _g 2.3% ^at 2 ° ₃ L of 0.8% Cr, 2% Baoju 0.25 % Cej 0,2 Fe ^ j 0,13%

Hf, 0.1% Hf, and 75.4% TiO ₂ ) at 490-30 ° C at 1400 h ^-1 . The yield of malannic anhydride is 48%, calculated on the input hydrocarbons.

Example 2

A total of 10% (v / v) to the reactor was fed with a strongly acidic cation exchange resin in the H-form (based on a sulphonated polydivinylbenzenethylene resin). a phosphate catalyst (15% ^ρ 2 ° 5 per SiO 2) of a cylindrical shape (4.5 x 4.5 mm) heated to 80-2 ° C is continuously fed ¹ -1 (350 g / cm 2 h) substantially o 1,3-butadiene o-poor pyrolysis of C 4 -fracoia (47% by weight of isobutene, 1.1% by weight of butadiene, 27.6% by weight of butene, 6.8% of ois-2-butene, 7.4% tran-2-butene, 6.4% wt. of n-butane, 2.9 $ wt.% isobutane, and 0.8 wt. mixture of propylene - propane), together with 110 gl ^ +. h ^"1 aqueous of a solution of tert-butanol with a cono 50 wt. The crude reaction product is packed onto a distillation column, with liquid products containing substantially tertiary butanol (≥ 94% by weight), a small amount of diisobutenes and a small amount of lower alcohols, which are either used directly or lead to rectification and a portion * on the reocular after addition of water. Thus, it produces about 208 tert-butanol.

The top of the column is mixed with hydrocarbons, containing (by weight) 3.4 isobutene, 1.9 butadiene, 50.3 1-butene, 12.4 ois-2-butene, 13.5 trana-2-butene, 11, 7 n-butane,

5.3 isobutane and 1.5 propane - propane. Thus, the conversion of isobutene is about $ 96, butadiene about 5% butene-1 is about 0.2% and 2-butenes about 0.5%.

The hydrocarbon mixture is then similar to that of Example 1 with an air balloon of up to 1.4% by volume of hydrocarbons and in addition to the oxygen catalyst, as described in Example 1, at a temperature of 490-30 ° C, the yield of malannic anhydride calculated on reaches about 45 # ·

Claims (3)

OBJECT OF THE INVENTION Process for the production of tert-butanol and maleic anhydride from pyrolysis C 1 -fracoil, and preferably de-freed butadiene, characterized in that the pyrolysis C 1 -fracoil is introduced together with water, preferably in the form of water vapor, at a temperature of 40 to 160 ° C, preferably 50 to 120 ° C, in contact with a so-called " an amino acid, preferably a long-acid cation exchanger, at atmospheric pressure of up to 10 MPa, preferably 0.5 MPa to 3 MPa, wherein a hydrocarbon mixture is separated from the formed reaction product, substantially free of isobutene by reaction with water to tert-butanol, The tert-butanol is preferably recovered from the reaction product, preferably by rectification, and the hydrocarbon mixture is, in addition to the added gas containing oxygen, preferably air or oxygen, optionally also mixed with water vapor at a temperature of 350 to 650 ° C. C, preferably 400 to 550 ° C, to the oxidation catalyst, wherein the maleic anhydride is isolated from the reaction mixture in a known manner and the unconverted hydrocarbon mixture is preferably re-recirculated or at least a part of it is discharged for combustion. 2. The process according to claim 1, characterized in that the butadiene, preferably extracol, is separated from the reaction mixture after the hydration before the oxalate and the hydrocarbon residue is in addition to the oxidation to maleic anhydride. 3. The method of claim 1, wherein the water solvent is tert-butanol or a portion of the crude liquid product that is re-circulated.