CS204645B1 - Method for the separation of pure methyl-tertiary butylether - Google Patents

Description

It is an object of the invention to provide a process for the isolation of a slurry of methyl-tertiary-thiityl ether from three or more polyalcohols containing methanol and / or water and / or hydrocarbons and from 3 to 8 carbon atoms, optionally a diethyl ether which can be for the addition of organic substances having 1 to 6 carbon atoms which have at least one alkali and / or alkali in the non-lithium. dneíka that are chemically inactive went in com> pnentcoa and completely soluble in mettrnele, total or Staetoúne soluble - water ₉ vyiží having a boiling point of 80 DEG C. and added to azoo tropickoj Zaes methyl tcro- ^{<^} bαtyléter The methanol zvyžijú relative prohavert * methyl tert-butyl ether relative to methanol from <J12 -1 to yellow - like 2 ·

204-645

204. 645

The present invention relates to the isolation of pure methyl tert-butyl ether from mixtures containing mainly methanol or water or from multi-ring mixtures, in which, in addition to methyl and methanol, water and / or maleate are present. hydrocarbons having from 3 to 8 carbon atoms.

Methyl tert-butylbutyl ether (2-methoxy-2-nioeylpropane) is produced by the addition of methanol and isobutene. The reaction balance is all the more favorable for the formation of methyl tert-butyl ser, which is lower temperature and higher pressure. However, the temperature decreases as the temperature decreases and therefore the synthesis is carried out using suitable catalysts. Such are, for example, sulfuric acid, Louis acids and, in particular, sulfonated ion exchangers. The H-forrae resins, which are particularly effective, are mainly sulfonated copolymers of styrene, and di-vinylbinin and sulfonated polyolefins. The reaction temperature is generally 50 to 100 ° C and a pressure of 1 to 4 MPa. It is necessary to feed pure isobulene, a Cíf k a o stad stage, which is obtained in the ordinary process of treating the pyrolysis gases or cracking gases. Isobutene, as a hydrocarbon, which has a double bond to the terrarium carbon, reacts from all the mono-phosphines to the other, so that, moreover, the dofins and even the conjugated dienes behave essentially as inerts. The equilibrium and rhalo-reaction may be controlled by an excess of some of the reactants, but it is not to be welcomed because the reaction mixture then contains either a large amount of isobutene in addition to other CG-dibodies and others. It is difficult to find a suitable treatment, or in methanol, which in turn is difficult to separate from the methyl tertiaryl ether because it forms an azeotropic mixture with it. However, C-. the hydrocarbons are relatively easy to separate from the motyl lithi-batyl ether by rectification and the methanol is stripped off by extraction with water (v. British Pat. 1 369 889 * 1 369 890; DOS 2 - 246 004 et al.). From the aqueous phase, the methanol is recovered by rectification and recycled to the medium. US Pat. 3,940-450, proceed as follows: ^{R is} removed from the reaction mixture isobutene, and then, the first azeotropic distillate is obtained as methyl ate-butyl ether ether distillate and excess methane as the distillate residue. Azeotropic mixture of methyl tert-butyl ether and methanol, but containing 15% by weight of methanol, is subjected to a second azeitropic agent, wherein dasattaasiblu-n-pentane, calculated on methanol, is added to the mixture. The distillate consists of a novel azaotripic mixture of n-pentane-metaad and a distillate residue of pure methyl-1-terathylether. Mixture of the mixture. and the methanol is then extracted with water and the two phases: the raffinate and the ε-coffin are separately treated with rectification to give pure n-pentane and methanol. In Brit. pat. 1 054 747 dilutes the separation of the alkyl-vinyl ether from the mixture with alcohol-extractable liquid _{9 by} contacting it with β water, but with a phenol-water binder such as axtaxal thallium for alcohol.

The disadvantage of aqueous methanol eKtrakole withstand the meetlIι-ter »i-ЪutylLéa & iвд the fact * that gets wet _{motyl-teri-1bltylétor>} ^ ajne Oby which still contains a small navyžo mn> žetva methanol. Such methyl-methyl-tert-butyl ether added to the gasoline has the same effect

204 045 misting it and causing the niece the difficulty, especially in winter, by freezing the pipeline, and the same also applies to extractive distillation · using water or water-borne as an extractant. Removal of water from the butyl-toro-butyl ether It is difficult because they form each other azo o tropical · Salts of epéeob removal and η · -, tannol and the butyl-t-butyl ether using azeotropic n-pentane distillate is also difficult to load ·

The above-mentioned deficiencies are eliminated by the method of isolation of pure methyl toro-butyl ether with a two-component or multi-component salt containing methanol and / or water and / or hydrocarbons having from 3 to 8 carbon atoms, or di-ethyl ether in which the salt is subjected to extractive distillation. 0.05 to 0.2 MPa, preferably at atmospheric pressure, in the presence of an extractant having at least one oxygen and / or nitrogen atom purged in the molecule, which is chemically inactive against the component of the mixture and is free of water soluble methanol soluble in water And has a boiling point of 80 to 290 ° C, preferably 150 to 250 ° C, to the flax standard.

An advantage of the isolation method according to the invention is the high efficiency ¹ , this simplicity * and hence the low investment cost ^{1 of the} device, which is sufficient to dimension ¹ to work at atmospheric pressure or at near atmospheric pressure, lower energy consumption and availability warmth * stable oxtractive solvents ·

At atmospheric pressure by rectifying the mixture of methyl t-o-butyl ether with methanol containing 15% and more by weight of methanol, it is not possible to obtain pure methyl tert-butyl ether, at most only aseotropic roe containing 85% by weight of methyl tert-butyl ether. the motility of the tert-butyl ether in the azeotropic composition of the mixture is equal to one. The addition of the extractant to the aseotropic mixture affects the relative potency of the motyltorbutyl ether, thus making the major modsimolocal forces a model of methanol and an extractive agent. butyl ether (1) -methanol (2) - extractive agent (3), where the type of extractive agent changes, an objectively quantitative value is obtained to compare the efficiency of the extractive agent.

Relative performance values do not help to smell the equilibrium data of curves · - steam on the modified equilibrium pumping device fell Qlllespio ·

Extracting agents that produce a blister-borne methyl-tert-butyl ether ethanol hotoropenic systems (e.g., 1 ethylene glycol and otanelamine) are not scaled on the apparatus, therefore, the suitability * is demonstrated by direct experimental dsstilane, such as

These are given in Examples 1 and 4. Example 5 shows the values of the determined relative abrasion as the criteria for the effect of the extractive agent used on the extractive coating.

ZU4 '845

The aforementioned canary examples of extractively distillate metilMatai are useful, but merely illustrate what type of mtyl-tnre-kutylether and whatsoever to be given.

Example 1

The laberatore »J rectified and hardened, the town 25 deareti <dtýah floors and a forged axtraktivna distiláaía auesd discounted! 73.5% move and. mayl.t «ra-taritrlátaru, 20 <herding. aetanal, 3.5% herding, water and £ 3 tactile. iaabm-Unu so that my dad can be distilled from the bank of the bank, consider boiling and boiling at a height of 16 th. The decalcifying head is adjusted to a reflection level in order to adhere to the ethylene glycol and, instead, to distillate. The other head was 'defective' and the reflux was returned to the calons. tapping head of the carcase (54.5 ° C). Xsobtene escapes from the head of the gas, the distillate is collected from the washings and the untreated extracts Sulfur - atylene enylcol is taken up in a d ' flask. acquired dMtUlat dasahnja Sistatu 99.9 $ herding. meyl-tert-butyl ether, 0.05% flour, neetael, and 0.05%. .hn »t, iaabutene. .

Example 2

On 'tan isan sariadni aka in example 1 and otherwise rawnakýah padstekaah aa rabí delaaie taj read kidnap aka in example 1, only ointment atllona.Llkal is parivative in extractively! deesiláci! diжatlrlfonamid aka éinidla. A 99.9% strength of α-β-absahase is obtained. methyl tare-butyl ether aka prt. prvaj dastiásai.

Example 3

The upper J part of the Kalana has 16 tearate trays and has fallen with an unbelievable size of 16 taaretics at the same time as Example 1. Bactrakt & naj dasHá® !! sa padrabaja ravnaká snas aka in the example. 1 and 2. Extractively Sialdla sa pawžija taze-buiylakahal and reflected panar. · The distillate is added and analyzed separately. №Uvr ** í abeah tatyl'taeзa * * »butllé1éxu palatal distillate - 97, 2% by weight, which declines and decreases at the abatement of '84 J herding' ne-syl-tara-butyl ether distillate, in the flask aa nMehbdsa. up to one-third and most of the mylyl teryl ether. Nnqpak,. . abisah taca-butylalketal in the deacilate ras tle ad 0.3% by weight, and 14% kurt.

204 B4S

Example 4

The mixture contains 73.13 wt. in tert-butylethyl ether, 16.90% by weight of methanol, 8.80% by weight of isobutene, 0.25% by weight of diisobutene, 0.29% by weight of t-butanol, and 0.63% by weight of water, and subjects the extract to the distillate using ethanolamine as the extracting agent on the apparatus as in Example 1 · Amount of impregnated ethanolamine to the amount of distillate withdrawn It is 1.6: 1 and the roflux draft is 1: 2 * The distillate is divided into 3 fractions according to temperature: front fraction 22 to 54.5 ° C, middle Czakola 54.5 ° C, rear fraction 54.5 to 67 ° C. The main fracola is an etrodal fracola, which represents 100% methyl-tert-butyl ether and obtains a total of 85% by weight.

Example 5

The addition of the calculated amount of extractive agent so that its content in the toraeric potency is 68.7 mol% · The mixture ea flutters into a modified equilibrium oircular port according to gilleopia, lapses and boils, and equilibrate for 3 hours to achieve liquid-vapor equilibrium, and samples of liquid and vapor phase are taken, which are then analyzed by thromatographs and calculated and the relative yield of methyl tert-butyl ether relative to methanol. The eu results obtained are given in Table 1.

Table 1

Р «г * 4вт6 8í.lo mixture Relative prehavoot * 1 - Bttuel / 2 / 1 2 / 1 / - / Я / - propylAeelycol / 3 / 4.79 3 / 1 / - / 2 / - ммв1ж «ргор * 11о1аж4п / 2 / 7.18 * / 1 / · / 1 / - t »re-toutylalkohel 2.12 5 / 1 / - / 2 / - dlmtjrlfonnald / 3 / F 3.71

From the examples shown, it can be seen that otyleaglycol, prepolyglycol, atanolamine, lsepropanolamine 1 dimethylformoforms are excellent extractive agents for obtaining pure methyl toro-tratyl ether, extractively wetted with a mixture of methanol and methanol. where, as the third component, the toro-butanol and the above-mentioned compounds did not clarify (2.12), which also shows a change in the efficacy of ^1- tert-butanol as an attractive agent documented in Example 3.

204 645

The pure methyl tert-butyl ether in methanol contains more hydrocarbons (over 10% by weight), but it is possible to re-decrypt it or methyl-tert-butyl ether, which has been attracted by oxtractivity. ?

• One hundred rectifications.

Extractively Used The reagent contains via flow methanol and possibly water if present in the soil. The extractant reagent is reacted in a suitable manner. Sulfate as well as methanol, which is advantageously re-cycled to the synthesis of the butyl-toro-butyl ether.

Claims (2)

OBJECT OF FABRICATION® 1. A process for the isolation of pure methyl toro-butyl ether and / or Lobo multi-component mixtures containing methanol and / or water and / or hydrocarbons having from 8 to 8 carbon atoms, or a diethylether, characterized in that the abatement is subjected to an extractive pressure at 0. At atmospheric pressure, the presence of an oxtractive agent having at least one cyelic and / or nitrogen atom bound to the molecule, which is inactive with respect to the components of the mixture and is not water-soluble, is water-soluble and non-biodegradable; it has a normal boiling point of 80 to 290 ° C, preferably 150 to 250 ° C 2. The process according to claim 1, characterized in that two or more alcohols, preferably otylanelycol, propylene-olol, lyerel, aminoalcohols, preferably otanelamine, iaopropanolamine, alcohols, preferably toro-butyl alcohol and preferably toro-butyl alcohol are used as the extractant. dinotylfoxmamld.