CS225019B1 - The continuous production of methacrolleine and/or methacrylic acid - Google Patents

Description

The present invention provides for the continuous production of meeecrolein and / or meeacrylic acid in the gas or vapor phase from available petrochemical raw materials, using selective oxidation catalysts.

Known (Seeboth Η, Freiberg J, Lucky B: Chem. Techn. 30. 465 (197B); U.S. Pat. No. 3,423,329; Japanese Pat. No. 52-9651, 47-22 / 56) isobutene oxidation to methacrolein and, in the second stage, not to meeacrylic acid, to monocompatible oxide catalysts, in particular based on molybdenum, antimony, cobalt, iron. - potassium, bismuth, phosphorus, chromium, nickel, silicon. Despite the obvious advantages of the catalyst, the disadvantage is the need for pure isobutene as the starting material. In the case of the use of a butadiene-pyrolyzed C 1 -fract, besides meeakrolein, 1,3-butadiene and other compounds are also formed. A varied mixture withdraws the insulation and may adversely affect the life of the catalyst. The current production of 1,3-butadiene and mixtures thereof penakrolnínu oxidation of butene as a molecular kyslkkom príoomnossi hours of catalyzing ^{t -} ^ ob ^ Μθ MRA driving systems ^{10, 1-8} ^ ¹² - ^ '' ⁰ - ^^ - ^ ^'1 ^,! - ¹² ^ ⁰⁾ - ¹ ^ ⁰ - ⁰ -Λ ^^ ^{'wherein Q is} phosphorus, arsenic, boron, scrap; R is potassium, rubidium, cesium; x is the number of oxygen atoms corresponding to valencies of the hefty elements, it is solved in another way (jap. pat. no. 51-27859). However, in addition to the problems mentioned above, the catalyst is not sufficiently solved.

Recently, a number of shadowing maps have appeared. superficial. information on the production of methaclein, acid and peaylpenaacylate nididain teri-butylalkne, which was previously obtained by the selective hydration of isobutene from the decomposed -napped C4-fraction / Hasnike T, Matsuzawa H: Crushing Process. 52, No 2, 105 (1979); Chem. Engng. News 56. No 19, 16 (197 /) /, - the oxidation of tert -butyl alcohol with the benefit of water vapor is carried out in two 8 tons of time, but no data is available - catalysts; data on the production of methacrylic acid and / or 1,3-butadiene from a gas mixture containing clay are also known. oxygen, tert-butyl alcohol or isobutylene and / or n-butenes by blowing through the catalyst of the general formula

MoaSbbBicFedN-eCofXgYh ^, where

X = K, R b, C 1 and / or T 1;

Y = Se, Zn, Nb, V, Ru; ,.

.alpha. = 12 ;.

b = 0.2 to 20;

c, d, e, f =. 0.2 to 12;

g, h = 0.01 to 4.

In the latter case, the data on the low temperature oxidation of tert-butyl alcohol and isotobutyl tert-butyl ether to methacrolsine (or auto. zldPrice Elements II. groups, V.l>, Vl.Ji and VII.] l subgroups of the periodic system of elements. In both cases, however, the problems are also due to the low-melting catalyst and the resulting lower life-cycle. On the other hand, it is also known to prepare homogeneous multi-bed oxide catalysts (Ci. Author. No. 185 016, GDR Pat. No. 128 3501), but only for the oxidation of gas-phase defins, in particular propene to acrolein and isobutene to oSakkbtein. , reip. amc) onooidation. isobutene to methylcyclohexylmethylene and deoxide dehydrogenation of n-butenes to 1,3-butadiene.

Finally, it is interesting to note that ipftiob (or the author's publication No. 212 584) of the production of meeakrolein and / or acetic acid is also tert-butyl compounds on a MooB4FecXaSieK4g oxide catalyst which, however, , despite many advantages,. it does not yet exhaust all the essential substances, in particular, to oeeacrolein.

Thus, a number of known methods utilize and still exist the problems of producing 6.beta.-1 and / or oleaginous acid from petrochemical ureas to be solved by the present invention.

According to the present invention, iipdiob is produced by the crystalline production of mseakrolein and / or mercaptic acid by oxidation of tert-butyl organic compounds of ammonium or ipol and isobutene with cyanobenzene or oxygen-containing gases in a gas / steam vapor phase at a temperature of 200-550 ° C. with the addition of large steam to / or inert gas, with the catalytic λ element of the multi-component. oxide. especially molybdenum-based, bismuth-based catalysts to the main iron, silicon, potassium, chromium, cobalt and nickel promoter eyes, the reaction being carried out with a catalyst of the type "·

MoBi _b P _c Fe _d X _e Si _f O _g abcdefg where

Mo, Bi, P, Fe, Si k 0 molybdenum, bismuth, foifor, iron, silicon and oxygen,

X. It is KIPON one of the elements of the ikupiny encompassing a magnesium woman and an, d]? ιksl II ₉ chromium, cobalt, nickel, a, b, c, d, e, f, g znamenajd atomic ratios of the elements, wherein a is 8 to 16 e is 0.05 to 6, b is 0.1 to 2, f is 30 to 90, and c is 0.1 to 2, g has a value determined with respect to 10 and 10 = 1; kž 5, to atomic ratios of other elements.

The catalyst used according to the present invention differs in addition to the method of preparation and several other proportions of components in the oxide catalyst, in that it also contains phosphorus and also because these catalysts are applied to oxidize an aqueous solution of tert-butyl alcohol, isobutyl tert-butyl ether, diisobutenes. and other starting materials. This greatly expands. The possibilities of using a multi-component oxide catalyst, unlike many known ones, are homogeneous in structure and composition.

An advantage of the process according to the invention is the raw material availability and the simple possibility of obtaining tert-butyl organic compounds, in particular tert-butyl alcohol, primarily in the form of aqueous solutions from a mixture of α-olefins by selective hydration of isobutene on sulfonated bivalves. other acids, even from crude pyrolysis C 1 -fraction (US Patent Certificate No. 199 849) without the need to concentrate tert-butyl alcohol. Furthermore, the possibility of a simple high-selective production of diisobutenes (cf. No. 6,188,828), the production of isobutyl tert-butyl ether, this ether as well as diisobutenes are the donor of up to 2 molecules of the intermediate isobutene. Another advantage is the low energy consumption and the more efficient removal of the heat of reaction even in the in situ network in the forming water and, last but not least, the high selectivity for the desired products.

In addition to oxygen, air or other oxygen-containing gas, such as carbon dioxide 3, oxygen, low oxygen nitrogen, and the like, it is desirable to increase the activity of these gases by ozonization, additives, resp. preliminary partial formation of atomic oxygen. The tert-butyl organic compounds according to the invention include, in particular, tert-butyl alcohol, an aqueous solution of tert-butyl alcohol, isobutyl tert-butyl ether, sec-butyl tert-butyl ether and n-butyl tert-butyl ether, propyl tert-butyl ether , isopropyl tert-butyl ether, amyl tert-butyl ethers. In addition, diisobutenes and isobutene-isobutanol precursor can also be associated with them. The function of the inert gas can primarily be performed by water vapor, carbon dioxide, nitrogen, argon, helium, to a lesser extent carbon monoxide.

The oxidation products obtained are generally isolated. The main products, methacrolein and methacrylic acid are either the final product or monomer, but most often methacrolein is in addition to the oxidation to methacrylic acid by several known methods and methacrylic acid for esterification with alcohols or addition or polyaddition of oxiranes and alkyloxiranes. The isobutene formed is most often recirculated or isolated. Similarly, most commonly unconverted starting materials are recirculated.

In setting the molar ratios of the starting materials, not only the maximum selectivity is important, i.e.. j. achieving short contact times (usually from fractions of a second to 5 seconds), but also high production and oxidation safety, so it is important to respect the known explosion limits of gases and vapors.

Further details of the method of the invention as well as other advantages are apparent from the examples.

Example!

A 20 cnP catalyst tableted into 4 x 5 mm tablets having the following composition is placed in a reactor of 80 µm length and 25 mm internal diameter made of meltblown glass having the following composition: Mo ^ Bi ^ P ^ Mn ^ Fe ^ Mg ^ ^ Κθ 1 ^^ 43θχ · Raschig rings made of hot-melt glass are placed ^{under the} top and above the catalyst layer. ⁴

After the reactor has been heated to the desired temperature, an aqueous solution of tert-butyl alcohol together with oxygen-enriched air is fed to the top of the reactor such that the molar ratio of tert-butyl alcohol: water: oxygen = 1: 12.3: 2.7 at approximately constant tertiary catalyst loading. Butyl alcohol (ТВ).

The reaction product is cooled with a water condenser and collected in a separator, resp. in a lubricator, analyzes and divides, eventually leading to dooxidizing and processing ii, either to the alkyl esters of meeaacrylic acid, or to polyoxalkylene glycol monomethacrylates.

The results of the one-stage oxidation at risk temperatures are given in Table 1.

T a b u 1 'k a 1

re- load of A horse- Seletivity (%) of conversions producibility Akin catalyst version on the: eetaaroleíou temperature (° C) ^(kg TB ^m kaf ^h (%) meta- acid-isobu-acce-acetin meta-dehyd kry- hunting, A catalyst Цй1- _dioxide; (kg.rnT ^ h ^"1) Clt ^ e * ^at tert-butyl alcohol kroleín

340 320.0 100 37.1 0.6 56.7 1.0 0.6 3.9 115.8 360 318.8 100 72.1 1.3 14.2 1.2 1.4 9.9 184.2 380 309.8 100 70.6 1.7 11.6 1.4 1.0 13.7 195.0 420 307.4 100 64.6 1.3 8.9 1.8 2.8 20.6 172.6

Example 2 ^p ostu ^p U is the decorative and ^the s ^W hen ^the lacI ^1, with the only extended ^ elem the ^p ri temperature between approximately 3 ⁸⁰ ° C, the top of the reactor filled with catalyst § ^p eeCftnovarýe in example 1, is fed an aqueous solution of teri .butyl alcohol and air with oxygen in the molar ratio teri.butylalknhol: water:. O = 1: 12.3: 2.7, at a constant load catalyst terc.butylakkoholom 4 ° ^6, 1 · In those pndmienn ^of the tosiahne tonverzia teri, but ^{the y} lal Shaved 100 ^{g of} a piglet tivity transformation teri.butylaUcoholu ' ? (%) for: meteacolein 62.0; mmeakrylic acid 1.7; isobutene 26.4; acetone 1.6; acetaldehyde 0.9; rtillium oxide 7.4. Producibility eθkahk'oltínu to catalyze the ^ ^ ore in said ^p ndmikon ^to a ^218.1 gm ^of "\ ^h" '.

Example 3

The procedure is similar to that of Example 1, except that the temperature is constant

380 DEG C. and a ^p ribližne same loads tatalj ^ tore ^{Tert. -Butyl and} a ^co LHO ^l Oe as the bar contains ^yl Šlik in the air. For the conditions as i) the results obtained are summarized in Table 2.

Table 2 i W

I >>

I Konneezia t ^^ buty! (%) tlri.bttylalkllllt on: what ~ P * - alcohol and i м Λ (%) a team 'g и Φ ρ μ aJ m co Φ rH you -with * >> O я • Sfr P o rH P • H хя ρ 7q Д <0 P as 5 *about 0 Ю 5-g £ β Ρ φ а 03 o N M P Ф o a P Ф o O M

ΦО Φ OM ЯРДН

1: 12.3: 2.0 315.8 100 62.2 1.7 27.8 1.5 1.6 5.1 170.8 1: 12.3: 2.3 318.2 100 64.8 3.6 15.2 2.9 3.2 10.3 178.4 1: 12.3: 2.5 306.3 100 70.2 3.0 14.2 2.3 2.1 8.2 199.9 1: 12.3: 2.8 309.8 100 69.2 2.2 12.6 1.3 1.5 13.1 167.5

Example.

is similar to Example 1, except that at a constant temperature of 380 ° C and approximately the same catalyst tert-butyakoohooom catalyst load, the amount of water in the feed varies. The detailed experimental conditions as well as the results obtained are summarized in Table 3.

Example 5

The procedure is as in Example 1, with the only difference that the reactor of the specified ^Star Oo of ^p u ^tp ice 1 was placed ²⁰ cm ^{3 of} ata ^ly load, ore grading of 1-3 mm Composition Μο ° ^ 5B1 "* 0 ⁵ ° ^Ο 4 5 ^N1 2 ^ e ^^ Si ^ O *. ^The lavu In the reactor vyloriateřio ^t e ^p the lot 3, the ⁸⁰ ° C aqueous solution prJLvádza terc.butylalkoOolu airtight and enriched with oxygen so that the molar poměr'terc.butylalkoOol: water: oxygen = 1: 12.3: 2.3 and a retracted The tert-butylalcohol catalyst is 310.4 kg. Under these conditions, the conversion of tert-butylalcohol is 100%, the viscosity of the conversion of tert-butylalcohol to the mono-products is as follows (%: meeakrolein 59.1; methacrylic acid 3.5; isobutene 24.2 , acetaldeOyd 2.8, 3.2, acetone, carbon uiOičitý ^7, 1. ^b extravasation, wear ^of the ^profiles ata ^ate hours in the ^F or ^p ade is I68, ^4th

Table 3

Konnvezia tert-butyl alcohol («)

SeeEctivity (%) of tert-butyllakol on:

β M Φ • g about H sh C ABOUT β XD $ 4 • H й • P 34 на 3 what φ cO Λ P ω p about φ >> Φ N and 34 S • H

-P

what

1: 4,1: 2,7 295.0 100 65.8 1.2 10.8 2.1 0.8 '9.3 152.3 1: 12.3: 2.7 309.8 100 70.6 1.7 13.9 1.4 1.0 11.4 195.0 1: 16.5: 2.7 328.1 100 57.3 1.0 30.7 1.3 1.0 9.1 183.0 1: 23.3: 2.7 297.4 100 56.8 1.3 31.8 2.0 1.9 6.2 144.4

Example 6

The procedure is as in Example 1, with the only difference that do.reaktora Speeifikovan s ^{e o p} u ^tp ice ¹ was placed ²⁰ cm ^{to 3} ata ^{ate ly} of the crimping hours ⁵ x 5 mm with a composition of Mo Bi ^ q ^ 5 " ° ^{C 4} 5 2 ^{NL, SL} 3 5 ^FC 43 x ⁰ ·

For Olav vyhriateOo reactor at 430 ° C was fed an aqueous solution of a terc.butylalkoOolu AIR enriched kyslkkom such that the mole ratio terc.butylalkoOol: water +: O = 1: 12.3: ^2, 7 and a retracted totalyzdtore terc.butyto ^ Ohotom is 3V7 ^, O ^ 34¾ ³ ^^. ^{For the t} ^ y C ^t ° of the conditions, the conversion dosiaOne terc.butylalkoOolu 100%, the transformation ktivity see © terc.butylalkoOolu jednooiivé the product is the following (%: 49.57 meeakroleín; acid mmtakrylová 0.62 isobutene 41.94; acetaldeOyd 1.89, acetone, and 2,3 'carbon uiOicitý 3.68' producibility catalyst ^{life of the} H8, ⁴ l ^of W ^{acro eeím} a ^and r ^O · ¹ ·

The procedure is as in Example 1, with the only difference that the head of the reactor, filled with ²⁰ cm ³ tataŮ.yzátare épecifikovan ^ s ^tp la pr e ^{d 1,} · vylwiateho at 380 ° C was fed a mixture of iso-butanol, water, and air- oxygen-enriched so that the molar ratio of isob225019

Example 7

Under these conditions, isobutanol convection of 98.1% is achieved and the isobutanol conversion viscosity (%: meeakrolein 33.0; mm-acetic acid 0.7; isobutene 21.7; 1-butene 2.2; cis-2-butene б, б) trans-2-butene 5, 8, 1,3-butadiene 4.9, acetaldehyde 1.2, acetone 2.3, carbon dioxide 11.4.

example

The procedure is similar to that of Example 7, except that a mixture of isobutyl-tert-butyl ether, water and oxygen-enriched air is fed to the head of the 380 ° C reactor instead of isobutanol, so that the molar ratio of isobutyl- terc.bttyléter: water and oxygen = 1: 25.7: 5.3, and the catalyst load of isobutyl terc.butyééeeoom is ^{275, 0}

Under these conditions, the conversion of isobutyl-tert-butyl ether 100% and selectivity (%) to: meso-oline 31.5 is achieved; methacrylic acid 1.1; acetone 11.7; acetaldehyde 1.2; isobutene 34.2; trans-2-butene 4.8; cis-2-butene 3,3; - carbon dioxide б, 1.

Example 9 ^p of the grades is as in the pr ^ ladle ^{7, -} tan p ^{characterized} rzz ^d itlom ^z e reactor has taplotu 4 ²⁰ ° C - and the place of isobutanol was fed a mixture of diisobutene such that the molar ratio of diisobutene: H : tysltt = ^ 23.5: 4.9. The production of methacrolein on this alata is ^{7.5 kg} . m ^ t · ¹ ” ¹ ·

Claims (1)

Process for the continuous production of meeakrolein and / or mmealecylic acid oxidation of tert-butyl organic compounds alone or together with isobutene oxygen or oxygen-containing gas in the gas and / or vapor phase at a temperature of 200 to 550 ° C, typically in the presence of water vapor and / or inert gas, under the catalytic action of a multi-component oxide catalyst, in particular based on molybdenum, bismuth as the main constituents and iron, silicon, potassium, chromium, cobalt and nickel as promoters, characterized in that the reaction takes place with a catalyst of the type WcWf ° g wherein Mo, Bi, P, Fe, SL and O are molybdenum, bismuth, phosphorus, iron, silicon and oxygen, X is at least one of magnesium, copper, potassium, chromium when b is 0.1 to 2, c is 0.1 to 2, d is 0.5 to 5, e is 0.05 to б, f is 30 to 90 and g has a value determined in accordance with the conditions and atomic reminders of other elements.