SK282654B6 - Method for partial hydrogenation of aromates and/ or their partia l hydrogenation with hydration - Google Patents

Abstract

The method for partial hydrogenation of aromatic hydrocarbons and but also for their partial hydrogenation with conjugated hydration to cycloalkanols and/ or alkylcykloalkanols under 80 to 280 °C (130 to 200) is realised by hydrogen in one technological degree under the presence of organic additive substances (alkanols C1 to C4, glycols to polyglycols, halogenated to polyhalogenated hydrocarbons, carboxylic acids C1 to C4, ethers to crown ethers) or their mixtures with water, on the catalyst made of at least one metal of VIII. group of periodic system (precious metals and iron triad metals) or its compound as hydrogenating component, or besides of acid or extra-acid solid hydrating component (solid acids, respectively ansolvo acids, such as sulphonic polymers in the H form, zeolites activated to the H form, acidified alumosilicates with partly or completely amorphous structure, and things like that).

Description

Technical field

The invention relates to the partial hydrogenation of aromatics, in particular aromatic hydrocarbons, to the corresponding cyclic alkenes, and to the partial hydrogenation of aromatics conjugated with hydration to the corresponding cycloalkanols on technically readily available bifunctional or simultaneously two monofunctional catalysts under relatively mild reaction conditions.

BACKGROUND OF THE INVENTION

More recently, the relatively low selective hydrogenation of benzene to cyclohexene, whether on homogeneous or heterogeneous ruthenium catalysts, is known [Weissermel K., Arpe H. J .: Industrial Organic Chemistry, p. 302-303, Prague, SNTL (1984); Polievka M., Macho V., Uhlár L .: CS 194 977 (1979)]. However, according to these solutions, likewise, the hydrogenation of benzene to ruthenium in the steam-gas phase [EP 0055495, US 4,392,001] in the presence of water does not achieve sufficient benzene conversion and selectivity to cyclohexene which, moreover, is expected to decrease further with increasing benzene conversion. . And not only heterogeneous catalysts, but also metal complexes VIII. groups with sufficient selectivity do not catalyze the hydrogenation of benzene to cyclohexene [US 4,307,248, 5,254,763 and 5,457,252], which is quite understandable, since the aim of the processes of these patents is not to produce cyclohexene but to produce fuels with no or minimal content of toxic benzene, mainly by hydrogenation to cyclohexane. Moreover, although on a ruthenium catalyst [US 4,225,733], but as a reducing agent for the hydrogenation of benzene, molecular hydrogen is not used, but hydrogen iodide, which is hardly available for industrial application.

Other solutions have found modifications to the ruthenium catalyst or hydrogenation environment, as well as various methods for preparing supported ruthenium catalysts, including the sol-gel method [Niwa S. et al .: J. Chem. Technol. Biotechnol. 36, 236 (1986); Mizukami F. et al., Stud. Surf. Sci. Catal. 31, 45 (1987); Lopez T. et al .: J. Catal. 136, 621 (1992); Niva S. et al., Chem. Soc. Jap. 2, 105 (1990), EP 220,525]. On non-ruthenium catalysts, only cyclohexane is formed by hydrogenation of benzene [Murzin D. Ju. et al .: Chim. Think. (9), 654; (1989) Jermakov Ju. I. et al., J. Mol. Catal. 49 (2), 121 (1989)]. The partial hydrogenation of the aromatics is also carried out in the presence of water, with zinc sulfate being present in addition to mercury or its compound. So eg. Benzene produces cyclohexene and cyclohexane [Nahagara H., Kohishi M .: Jap. 62 81331; Jap. 62 81332; US 4,495,372], as well as in addition in the presence of bases, in particular alkali [Asahi Chem. Industry Co Ltd.: Jap. 59,186,929; 59,184,138; Tary Ind. Inc .: Jap. 58 74,621; Odenbrand CH et al., J. Chem. Technol. Biotechnol. 30 (12), 677 (1980)]. Even in the liquid phase in the presence of water and ruthenium deposited on barium sulfate and additionally doped with at least one of iron, cobalt, silver and copper compounds [EP 214 530]. A similar situation is also known in the gas phase hydrogenation of benzene or other aromatics and when the hydrogenation of benzene and other aromatics was also performed on Ni / NH ₄ - montmorillonite, only the corresponding cycloalkanes without cycloolefin additions were obtained [Lin Xiping et al. : Shiyou Yueba, Shiyou Jiagog 1989 f (1), 45] as well as on ferrous catalysts, respectively. dispersed iron on zeolite [Rastoji Ashutost: J. Indian Chem. Soc. 65 (12), 838 (1988)]. Thus far, the monocyclic aromatics have been partially hydrogenated to cycloalkenes only on various modified ruthenium catalysts [Klusoň P., Červený L .: Chem. Letters 88, 55+ (1994)] and not yet with satisfactory selectivity. Moreover, although many measurements were carried out in the presence of water with ruthenium catalysts, only cycloalkenes were received in addition to cycloalkanes. No conjugated hydrogenation in one reaction or process step was observed. The known published results are serious and explainable by applying not only catalysts but also other reaction conditions.

SUMMARY OF THE INVENTION

The present invention provides a process for the partial hydrogenation of aromatics and / or their partial hydrogenation with hydration to cycloalkenes and / or cycloalkanols in liquid and / or vapor phase, at elevated hydrogen or hydrogen-containing gas pressure, at a temperature of 80 to 280 ° C to heterogeneous and / or heterogeneous, and / or modified heterogeneous catalyst, such that it is carried out in one technological step in the presence of at least one organic excipient or a mixture thereof with water, on a catalyst consisting of at least one metal and / or at least one metal compound VIII. groups of the periodic system as a hydrogenation component or in addition with an acidic to super-acidic hydration component consisting of a solid acid and / or an ansolic acid.

An advantage of the process according to the invention is the partial hydrogenation of aromatic hydrocarbons also on other metals VIII. groups and their compounds except ruthenium, even on metal triad metal catalysts and their compounds. Then based on all elements and compounds of elements VIII. groups, including ruthenium, perform not only partial hydrogenation of aromatics to cycloalkenes in one technological step, but also hydrate to the corresponding cycloalkanols. Such extraordinary flexibility allows a process not only to produce cycloalkanes, but especially cycloalkenes or at the same time cycloalkanes with cycloalkanols or only cycloalkanols. Last but not least, with high selectivity to convert aromatics to valuable products and the possibility to carry out the process on a standard hydrogenation plant.

The organic excipient is at least one compound selected from among halogenated and polyhalogenated hydrocarbon aliphatic alcohols, C] to C _5, and alkyl amines and tri- alkyl Cl to _C4, monoethylene glycol, diethylene glycol and polyethylene glycol, the average molar mass of 400 g mol ^1, propylene glycol and polypropylene glycol with an average molar weight of 700 g mol ^1, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, formic acid, carboxylic acid, C ₄ to C, and dimetylglykolétery dimetylpolyetylénglykolétery and crown ethers. When using nitrogenous adjuvants, especially in the case of partial hydrogenation with conjugated hydration, care should be taken to apply only in small amounts in order not to "dull" the acidity of the catalysts. A heterogeneous or heterogeneous catalyst is most suitable when it is bifunctional, i.e. if it contains a hydrogenation, but also an acidic to superacidic, hydrating component. In cases of partial hydrogenation alone, it is sufficient if it contains only one, ie the hydrogenation component, and the optional carrier may be inert. However, even for the purposes of simultaneous hydration-conjugated partial hydrogenation of aromatic hydrocarbons, separate hydrogenation and specific hydration catalysts may be present at the same time.

For hydration, according to the present invention, in the reaction medium in the form of liquid or vapor, water in an amount of 0.2 to 100 moles per mole of aromatic hydrocarbon or a mixture of aromatic hydrocarbons is required. A content of less than 0.2 moles is already economically disadvantageous. Greater than 100 moles can also be applied to the process of the present invention, but is already technically disadvantageous because it reduces the effective reaction space and increases the consumption of excipients.

The acid component of the bifunctional catalyst or the particular acidic to supersacidic catalyst comprises at least one of the ansolic acids or solid acids, such as activated natural and synthetic zeolites, especially in the H-form and high modulus, sulfonated polymers and copolymers, especially in H-form and perfluorinated polymers. Furthermore, by acidification, in particular aqueous solutions of mineral acids or halogenated hydrocarbons, natural and synthetic aluminosilicates, kaolin, alumina, calcium and magnesium alumosilicates, calcium-magnesium-aluminosilicates, heavy metal oxides, oxides, in particular technical oxides of transition metals and metal sulphates. , III., V. and VII. groups of the periodic system.

In the case of liquid acids, the hydrogenation catalyst comprises at least one noble metal VIII as the hydrogenation component. group or compound. For metals and metal compounds of the iron triad, liquid acids are poorly effective or unsuitable.

The process according to the invention can be carried out continuously, semi-continuously or continuously.

Other non-limiting data as well as other advantages are apparent from the examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

To a stainless steel autoclave with a volume of 120 cm ^3, equipped with a propeller mixer (speed 350 rpm ¹⁾ Weigh 1 g dealuminated mordenite with a modulus of SiO ₂ / Al ₂ O ₃ = 72. This zeolite is previously dealuminoval in step 6 with hydrochloric acid with a concentration of 0.05 to 0.5 wt. %, gradually increasing the concentration in each step, using a five-fold excess of aqueous hydrogen chloride solution to theory, at room temperature, in each step for 5 h. Each step is followed by calcination at 450 ° C for 8 h.

Next, 0.15 mol of alkene or cyclohexene and 50 g of water are added to the autoclave in a series of experiments. Nitrogen is then introduced to a pressure of 3 to 7 MPa, depending on the desired reaction temperature so that at the reaction temperature the total pressure reaches 10 +0.5 MPa. Thereafter, the autoclave is heated to the desired temperature for 10 to 20 minutes with stirring and maintained at this temperature for 4 hours. The sampled and total product were weighed and analyzed by gas-liquid chromatography.

In a second series under otherwise similar conditions, however, a partial hydrogenation of the benzene conjugated to the hydration of the apparently intermediate cyclohexene to cyclohexanol is carried out. Therefore, instead of nitrogen, hydrogen is introduced into the autoclave and, in addition to the acidic mordenite, 0.15 g of microsuspensioned or partially sulfane-poisoned metal VIII is added. group of the periodic system, usually prepared by thermal decomposition of their carbonyl in an inert atmosphere to produce micropowders to pyrophoric properties followed by the action of gaseous sulfane. In addition, 2 g of organic polar polar additive are added to each experiment. Further conditions and results of both series of experiments are summarized in Tab. First

Example 2

Weigh 1 g of a bifunctional Ru-mordenite catalyst into the autoclave as described in Example 1. This was prepared from the mordenite prepared as described in Example 1, which was further converted to ammonium hydroxide by ammonium hydroxide. This was further impregnated with an aqueous solution of hexa-aminoturic chloride, then dried and reduced in methanol suspension at 150 ± 5 ° C, hydrogen pressure of 5 ± 0.3 MPa for 4 h. The bifunctional catalyst obtained contained 0.25 wt. % ruthenium.

0.15 mol of aromatic hydrocarbon, 50 g of water and optionally a polar organic excipient are added to the autoclave. After the autoclave is closed and the air is removed, hydrogen is supplied to a pressure of 3 to 5 MPa, depending on the reaction temperature so as to reach a total pressure in the autoclave of 10 + 0.5 MPa. Further reaction conditions and results of the partial hydrogenation of aromatics to cycloalkenes and their conjugated hydration to cycloalkanols are shown in Tab. Second

Tab. 1

Starting unsaturated compound Hydrogenation component (metal) Excipient Reaction temperature [° C] Conversion [%] of the starting compound Selectivity [%] to cyclohexene Selectivity [%] to alkanol or cyclohexanol 1-hexene 200 40.2 > 99 1-octene 200 32.2 > 99 1-decene 200 22.1 > 99 1-dodecene 200 14.1 > 99 1-tetradecene 200 12.6 > 99 1-hexadecene 200 10.2 > 99 cyclohexene 200 28 > 99 cyclohexene 180 21 > 99 cyclohexene - 150 6.5 > 99 benzene Ru - 200 38 34 2.3 benzene Ru ethanol 200 43 18 32 benzene Ru tert-butyl alcohol 160 24 16 36 benzene Ni methanol 200 37 12 27 benzene fe ethanol 200 26 13 17 benzene Ru diethyl ether 200 54 15 43 benzene What ethanol 200 32 12 17 benzene Ru dimetyldiglykoléter 200 44 20 44 benzene Ru Crown ether 200 45 19 43

SK 282654-6

Table 2

aromatic hydrocarbon temperature [° C] Reaction time [h] auxiliary kind of substance wt. % aromat Aromatic conversion [%] Selectivity [%] for: CEN COL CAN benzene 150 4 40 83 8 9 benzene 150 8 44 82 8 9 benzene 170 4 56 70 17 12 benzene 170 8 57 65 20 14 benzene 200 4 65 53 32 15 benzene 200 8 67 49 35 15 benzene 150 4 methanol 2 45 82 15 3 benzene 150 4 methanol 4 46 80 18 2 toluene 150 4 - - 26 54 ^a 8 ^a 35 toluene 150 4 ethanol 2 37 48 ^a 31 ^a 20 benzene 200 4 PGOL 2 64 48 34 18 benzene 200 4 PRGOL 3 46 64 21 15 benzene 200 4 ETGOL + MIN 0.9 +0.1 42 66 18 16 benzene 200 4 DMGOLE 2 49 59 30 11 ethylbenzene 200 4 Degol 1.5 46 44 ^p 18 ^p 38

PGOL - polyethylene glycol PRGOL - propylene glycol ETGOL - ethylene glycol MIN - monoethanolamine DEGOL - diethylene glycol

CEN - cycloalkene

COL - cycloalkanol

CAN - cycloalkane

DMGOLE - dimethylene glycol ether ^and selectivity to methylcyclohexene and methylcyclohexanol ^b selectivity to ethylcyclohexene and ethylcyclohexanol

Example 3

Nickel (II) chloride is deposited on the mordenite with module 72 in the H-form, as described in Example 1, under vacuum at 450 ° C for 3 h, which is further reduced with hydrogen similar to the ruthenium catalyst in Example 2. The bifunctional catalyst obtained contains 0.11 weight. % nickel.

The catalyst thus obtained is applied to the partial hydrogenation of aromatic hydrocarbons, conjugated to the hydration of cycloalkenes to the corresponding cycloalkanols. The feed to the autoclave specified in Example 1 consists of 0.15 mol of aromatic hydrocarbon, 50 g of water, 1 g of said bifunctional catalyst containing 0.11 wt. % nickel and optionally excipients. Additional conditions of isochronous experiments (4 h) and the results obtained are summarized in Table. Third

aromatic temperature auxiliary substance conversion Selectivity j%] to: hydrocarbon [° C] kind of weight. % aromat [%] Aromatic. hydrocarbon CEN COL CAN benzene 150 - 12 48 13 39 benzene 170 - 24 35 22 42 benzene 180 - 36 29 34 37 benzene 200 - 43 24 40 35 benzene ³ 150 - 5 50 8 41 benzene ^b 150 18 31 15 54 benzene 180 PPGOL 2.5 48 27 44 28 benzene 200 Degol 3 47 28 43 29 benzene 200 TA + EOL 0.1 + 3 44 30 42 28 benzene 200 TE-MOL 0.1-3 43 32 40 28 benzene 200 TB + EOL 0.1 + 3 42 36 35 29 benzene 200 DI-MOL 0.1 + 3 42 37 34 28

^a reaction time of 2 h ^b reaction time of 8 h

PPGOL - polypropylene glycol 600 TA + EOL - triethanolamine + ethanol TE + MOL - triethylamine + methanol TB + EOL - triisobutylamine + ethanol DI + MOL - diisopropylamine + methanol

Example 4

The ammonium form of mordenite with module 72 is treated with an aqueous solution of 2% by weight hexaminonic nickel nitrate. %, in an amount of 100 cm ³ per g of ammonium form of mordenite. It is then dried and reduced in a methanol slurry at a hydrogen pressure of 5 MPa and a temperature of 180 ° C for 5 h.

It is then filtered, dried and calcined at 500 ° C for 5 h. Then, 1 g of the bifimulation catalyst thus obtained, containing 1.35 wt. % nickel, 0.05 wt. % copper and 0.03 wt. % cobalt is loaded into the autoclave; furthermore, 0.15 mol of aromatics, 50 g of water and optionally an organic auxiliary. The results of the isochronous experiments (4 h) carried out at a temperature of 150 + 2 ° C and an initial pressure of 5 MPa of hydrogen (at room temperature) are summarized in Tab. 4th

Example 5

Weigh 1 g of a comminuted commercial reforming catalyst containing 0.35 wt. % platinum and 0.35 wt. % rhenium predominantly on alumina. 0.15 mol of aromatic hydrocarbon, 50 g of water and optionally an organic auxiliary are added. The reaction temperature was 150 + 2 ° C and the time was 4 h. The further procedure is similar to that of Example 4. The results obtained are summarized in Tab. 5th

Tab. 4

Aromatic hydrocarbon auxiliary kind of substance wt. % aromat Conversion [%] of aromatics. hydrocarbon Selectivity % on the: CEN COL CAN benzene - - 39 2.1 0 97 benzene CC1 ₄ 1.3 21 35 7 58 benzene CC14 2.6 7 44 0 56 benzene CC1 ₄ 3.9 4 47 0 53 benzene CC1 ₄ 0.5 36 28 11 61 toluene CC1 ₄ 2.6 5 30 4 66 benzene CCU + DIN 1.3 + 0.1 23 36 8 56 benzene CCU + DIN 1.3 + 0.1 24 36 7 57 DIN - diethanolamine Tab. 5 aromatic auxiliary substance conversion Selectivity [%] for: hydrocarbon kind of weight. % aromat [%] aromat. hydrocarbon CEN COL CAN benzene - - 46.3 10 0 90 benzene KO 4 29.4 12 20 68 naphthalene KO + EOL 4 + 10 30 11 28 61 benzene ¹ KO 4 35 10 37 53 methylnaphthalene ¹ KO-MOL 4 + 10 31 10 29 61 benzene ¹ KO + KM 4 + 0.5 31 10 32 58 KO - acetic acid EOL - ethanol MOL - methanol KM butyric acid ¹ The catalyst was acidified by addition of the preliminary calcination under vacuum at 350 ° C for 3 h with an aqueous solution of 0.5 wt.

hydrochloric acid, dried and re-calcined at 300 ° C for 2 h.

Example 6

The acid heterogeneous alumosilicate catalyst is prepared from bentonite, consisting of 75 wt. % montmorillonite, 22.3 wt. % glassy phase and 2.7 wt. % of quartz. This bentonite has a burning loss of 8 wt. % and its analysis is as follows (in wt.%):

SiO ₂ = 69.55; Al ₂ O ₃ = 16.89; Fe ₂ O ₃ = 1.95; TiO ₂ = 0.19; MgO = 2.85; CaO = 0.20; Na ₂ O = 0.15; K ₂ O = 0.22.

The bentonite slurry in water, de-sanded by hydrodynamic separation, is activated (acidified) in three stages by extraction with hydrochloric acid at a total concentration of 2 M at 97 ° C for 8 h. After cooling and filtering the suspension and washing with demineralized water, the wet filter cake of the suspension is compacted using an extruder. The obtained extrudates are dried at 60 ± 5 ° C and dried at 105 ± 5 ° C to a constant moisture content of 1-2 wt. % water. The rollers of the extrudate thus produced are an efficient acid to super-acid heterogeneous catalyst. 0.5 g is taken from this, impregnated with an aqueous solution of palladium chloride and an aqueous solution of native chloride, and dried at a temperature of 100 to 150 ° C. Contains 0.4 wt. % palladium and 0.1 wt. % rhenium. It is then triturated to a fine powder and an additional 1 g of triturated only acid catalyst is added. Both are placed in the autoclave specified in Example 1 together with 50 g of water and 3 g of ethanol. Hydrogen is then introduced at a pressure of 80 bar and the catalyst is activated at a temperature of 150 ° C. Then, the autoclave is cooled, the hydrogen is discharged from it, 0.15 mol of aromatic hydrocarbon is pumped into the autoclave and hydrogen is again supplied to a pressure of 5 MPa. Then the autoclave is heated to 150 + 2 ° C and the experiment is carried out for 5 h. Further reaction conditions and achieved results are summarized in Tab. 6th

SK 282654-6

Tab.6

aromatic Another excipient hydrocarbon kind of weight. % aromat benzene benzene benzene dimethylnaphthalene benzene propylene glycol propylene glycol + butanol methanol + acid. acetic methanol + acid. sulfuric 2 5 + 2 10 + 2 5 + 0.5

conversion Selectivity [%] for: [%] aromat. hydrocarbon CEN COL CAN 47 22 24 52 49 23 31 46 39 29 22 49 41 29 21 50 48 22 31 47

Industrial applicability of the invention

The process according to the invention is applicable in the chemical industry, in particular in the production of cycloalkenes from aromatic hydrocarbons, in particular for the production of cyclohexene and in particular cyclohexanol from benzene in one process stage.

Claims (5)

PATENT CLAIMS Process for the partial hydrogenation of aromatics and / or their partial hydrogenation with hydration to cycloalkenes and / or cycloalkanols in liquid and / or vapor phase, at elevated hydrogen or hydrogen-containing gas pressure, at a temperature of 80 to 280 ° C, to heterogeneous and / or a heterogeneous, and / or modified heterogeneous catalyst, characterized in that it is carried out in one technological step in the presence of at least one organic auxiliary or a mixture thereof with water, on a catalyst consisting of at least one metal and / or at least one metal compound VIII. groups of the periodic system as a hydrogenation component, or in addition with an acidic to super-acidic hydration component consisting of a solid acid and / or an ansoleic acid. The process according to claim 1, wherein the organic excipient is at least one selected from halogenated to polyhalogenated hydrocarbons having from 1 to 5 carbons, aliphatic alcohols having from 1 to 5 carbons, alkyl to trialkylamines with alkyls, and number of carbons 1 to 4, monoethylene glycol, diethylene glycol to polyethylene glycol having a molar mass of up to 400 g molar ¹ , propylene glycol to polypropylene glycol having a molar mass of up to 700 g of molar ¹ , monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, Cisopropanolamine; to C ₄ , dimethyl glycol ethers to dimethyl polyethylene glycol ethers and crown ethers. Process according to claim 1 and 2, characterized in that in the case of partial hydrogenation of aromatic hydrocarbons conjugated to hydration to cycloalkanols and / or alkylcycloalkanols, 0.2 to 100 moles of water per mole of aromatic hydrocarbon or mixture is introduced into the reaction medium. aromatic hydrocarbons. Process according to claims 1 to 3, characterized in that the catalyst is bifunctional, comprising, in addition to the hydrogenation, also a hydration component and / or is formed by the simultaneous presence of a separate hydrogenation and a particular acidic to super-acidic hydration catalyst. The process according to claims 1 to 4, characterized in that the acidic component of the bifunctional catalyst and / or the particular acidic to superacidic catalyst comprises at least one of the solid acids and / or ansolic acids selected from activated natural and synthetic zeolites, sulfonated polymers in H-form. , perfluorinated polymers, acidification activated: natural aluminosilicates, synthetic aluminosilicates, kaolin, alumina, calcium and magnesium aluminates, calcium-magnesium aluminates, calcium-magnesium alumosilicates, heavy metal oxides, transition metal oxides, transition metal oxides II., III., V. and VII. groups of the periodic system.