TW387872B - Preparation of aliphatic alpha, omega-diamines - Google Patents

Description

V. Description of the invention (1) The present invention relates to a method for preparing an aliphatic α, Ω-diamine, which is hydrogenated from an aliphatic α, Ω-dieye in the presence of a catalyst, including the use of a hydrogenation catalyst (a) iron containing 'Or iron-based compounds, or mixtures thereof, (b) Based on (a) 0.001 to 0% by weight based on 2, 3, 4 or 5 promoters selected from the group consisting of aluminum, silicon , Hafnium, titanium, and vanadium, and (c) 0 to 0.3% by weight based on (a) compounds based on alkali metals and / or alkaline earth metals. The present invention also relates to the use of a substance containing the components (a), (b), and (c) as a catalyst for the preparation of aliphatic α, Q-diamine from aliphatic α, Ω-dionitrile hydrogenation.

Weisserme 1 / Arpe, Industrielle Organische Chemie,

Verlag Chemie, third edition, 1988, p. 266 reveals that hydrogenation has been carried out with an iron catalyst in the presence of helium under high pressure conditions to obtain hexamethylenediamine, which is used to make nylon (ny 1 〇η)-6, 6 Important fiber intermediates. Important conditions for suitable iron catalysts include high mechanical strength, long flow time, high space-time yield of hexamethylene diamine and complete conversion of hexamethylene diamine and 6-amino hexamethylene diamine and hexamethylene Diamine yield and very low levels of unwanted by-products. _ These unwanted by-products are formed in varying amounts, depending on the catalyst, to be separated from the desired diamine product. 'For example, hexamethylene diamine is hydrogenated to hexamethylene diamine, and the by-product is especially 6-aminohexamethylene diamine (ACN)' tetrahydroazepine (ΤΗΑ), 1 ~ amine cyanocyclopentene (ICCP), 2-Aminomethylcyclopentylamine (AMCPA),] = ~

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V. Description of the invention (2) Aminocyclohexane (DCH) 'and dihexamethylenetriamine (bhmTA) ° US-A 3 6 96 1 53 reveals that AMCP A and DCH are extremely difficult to communicate with hexamethylenediamine Separation. Large amount · AMCPA ’DCH and THA require many steaming halls, resulting in considerable capital and energy costs. US-A-4,2 82,38 1 'Second block, Table 1 reveals that hydrogenation of hexamethylene diamine to hexamethylene monoamine in the presence of an iron catalyst, with by-products in particular an average of 2400 to 4000 ppm 1,2 -Diaminocyclohexane, 1000 to 300 ppm of 2-aminomethylcyclopentylamine, tetrahydroaza mask at 2000 to 900 Ppm; and 2000 and 5 〇〇〇ppm6_ amine group. Example 1 of DE-A-2 429 293 reveals the presence of diazepam at five times the weight (under 93 to 98 C (reactor inlet temperature) or at μ to 104 ° C (outlet temperature) with a magnet The iron catalyst prepared by the mine is reduced and hydrogenated by hydrogen and doped alumina, silicon dioxide, calcium oxide, and vanadium pentoxide to produce 98.22% hexamethylenediamine, which contains 190 ppm 1,2_ Diamine cyclohexane, Example 2 reveals that the diazepam is in the presence of five times the weight of ammonia at 93 to 98 t (reactor inlet temperature) or at 94 to 104 C (outlet temperature) & Labrad〇r hematite The iron catalyst prepared by (FeA) is hydrogenated with hydrogen and doped alumina, silica and procalcium oxide to produce 98.0 5% hexamethylenediamine, which contains 350,000-1,2-diaminocyclohexane. '' One of the objects of the present invention is to provide a method of α, Ω _ two eyes in the presence of a catalyst (hydrogenation to α, Ω-diamine, without the above disadvantages, and can be technically simple and economical on the catalyst stream for a long time. With high selectivity. We have found that this purpose can be achieved by the methods defined at the beginning and the uses defined at the beginning.

V. Description of the invention (3) The catalyst of the method of the present invention and the use of the present invention preferably has a β ET surface to 20 square meters per gram 'total pore volume of 0.05 to 0.02 ml / g, and an average pore diameter of 0.03 to 0' 1 micron, and 0.01-0.1 micron pore volume fraction is in the range of 50 to 70%. f # 物 （The percentage of% is based on the 7L element and weight percentage% of the metal test and soil test metal oxide. Gonggou oxidation in the preferred catalyst precursor, the composition is preferably 92 to 99% by weight, iron oxide &Amp; a I to 100% by weight, a mixture thereof. It is preferred to use synthetic or dioxo-depleted iron hydroxide, or iron 'or iron oxyhydroxide, such as limonite;' J of iron oxide, hydroxide In the ideal case, # $ hematite can be used, preferably magnetite. In Fan Xin of H⑴.45: 1, it is said that for iron atoms, ㈣ is preferably equal to u3: 1, which is pure magnetite. ..3: 1 to 1.4: 1: Magnetite, which can be jealous of very pure „two f and / or iron (IΠ) compounds, or added in the form of extremely pure iron (11) compounds Starting material, and then doping the element to suit the chemistry of the 3: 3 catalyst, i.e. the dendron catalyst precursor is preferably produced, "denier I, preferably 0.01 to 0.2% = (b) contains 0.001 to 'based on 2, 3, 4 or 5, compared with | 3 miles ^ is 0. (Π to 0.1% by weight of the accelerator · Zuo ρ as good as J 4 or 5, combined with Α Shishi combination aluminum, Shi Xi, wrong, Titanium and vanadium are selected from the elements ^ e In addition, the catalyst precursor is better than white, 0.2 to 0.2% by weight, and ^ other Γ component (0 contains 0 to 0.3% by weight selected from the following metal or soil test metal = 0 weight, based on carp ' Sodium, potassium, zinc, and vanadium, especially aluminum, silicon, and titanium. V. Description of the invention (4) Cesium, magnesium, and calcium, preferably calcium and / or magnesium. The catalyst of the present invention may be a carrier or Unsupported catalysts. Examples of possible support materials are porous oxides such as alumina, silica, aluminosilicate, lanthanum oxide, titania, zirconia, magnesia, zinc oxide, and zeolites, and activated carbon. , Or a mixture thereof. The preparation is generally made by precipitating the component (a) precursor, if necessary, with the precursor component (b) precursor, and if necessary, with the component (c) precursor, in the carrier material ( (Depending on the type of catalyst required) In the presence or absence, if necessary, the resulting catalyst precursor is processed into an extrudate or ingot, dried, and then calcined. The supported catalyst can also be generally composed of the component (a), ( b), and if necessary, the solution of (c) is saturated The ingredients can be added simultaneously or successively, or can be obtained by spraying ingredients (a), and (b) and (c) on the carrier, if necessary, in a conventional manner. Suitable precursors for ingredient (a) are generally Water-soluble salts of easily available iron, such as nitrate, gaseous, acetate, formate, and sulfate, preferably nitrate. Suitable precursors for ingredient (b) are generally the above-mentioned metals that are readily available And semi-metallic water-soluble salts or complexes, such as salts, vapors, acetates, sulfonates, and sulfates, preferably nitrates. Suitable precursors for ingredient (c) are generally readily available The above-mentioned water-soluble salts of metals and alkaline earth metals, such as hydroxides, carbonates, nitrates, vapors, acetates, sulfonates, and sulfates, are preferably hydroxides and carbonates. Precipitation is generally carried out in aqueous solution.

5. Description of the invention (5) pH, or change the temperature. The temperature of the obtained catalyst precursor is generally 80 to 120, preferably 80 to 120. (: Drying in the range of temperature. Fox, roasting is generally 150 to 500. (: temperature in the range, preferably in the range of 200 to 45 () -C target range, in air or nitrogen flow. After calcination, the catalyst material obtained is generally exposed ("activated" ?, for example, at a temperature in the range of 20 to 50 (rc temperature 2J0 to 400_C), exposed to hydrogen pressure or containing argon and an inert gas f ( For example, the gas mixture of nitrogen) has a time in the range of 2 to 24 hours. The volume per small% of the sanitary speed is preferably 200 liters per liter of catalyst per hour. According to DE 24 29 293 (page 7 to 1) Line 12) is beneficial to add ammonia to the activated hydrogen. The activation of the catalyst generally excludes other required mixtures, such as air, in a reactor with a temperature in the range of 25 to 35 ° C. The gas content is preferably between 20 and 3 50 ° c. The standard catalyst can be used as a solid suspension catalyst. In the method of the present invention, the second step is to perform directly in the synthesis reactor, because the intermediate step, namely the passivation of the surface, uses oxygen-nitrogen in the general 20 to 80. . (: Temperature in the range, preferably at temperature. Then passivation catalysis The activation is preferably carried out at a temperature in the range of 180 to 500 ° C under the combined pressure, which is higher than the temperature within the range. The bed catalyst is used in the upflow or trickle mode, or the starting material used is below Aliphatic α, Ω- (I) 5 or 6 of the general formula I. Particularly preferred wherein η is 丨 to 丨. C: other than 2,

I

Page 10 V. Explanation of the invention (6) '-Nitrile, adiponitrile, pimelimonitrile, and suberonitrile Compound I is succinate, and most preferably diazepam. Particularly preferred is the use of hydrogenation in the presence of α, Ω-difluoride @ catalyst, which has less than two carbon atoms. Cyanide is added. ^ = = Obtained aliphatic α, Ω-dieyes, such as hexamethylene diphosphate, made from hydrogen phosphoric acid. Ester is present; 'from or in 3-pentaphthalene after nickel (0) compound and triaryl sulfide. Dezeng Zenggan-The stalk can contain trace amounts of phosphorus compounds, about 1 to 50 ppm, to serve 4 dishes, 2-dinitrile. When all or part of these phosphorus compounds are removed, the weight part of the compound is less than 5 ppm, preferably less than 1 P Pj. In the present invention, the catalyst time is extended. The weight of the phosphorus compound in the compound obtained in the method and in the method obtained in the application of the present invention, considering various conventional potassium chloride solutions ^ 'preferably extraction' to test (such as hydrogen sulfide sodium On the solution or hydrogen and oxygen, the second-flight treatment is 'adsorption or chemisorption', especially in the metal (such as iron) system, 3 is particularly good for distillation. The best is also for alkali metals and alkaline earth metals, lanthanum: # Periodic Table No. 1 1 A metal base of 1 a, 1 1 b and III b, such as calcium oxide, treats the two eyes. 'Ϋ́Τ' i 一 田 "is advantageously at a pressure of 1 to 100 mbar, preferably 10 to 2000 mbar In this case, diazepam is usually obtained as an overhead product, because the scale compound '1 is less volatile than diazepam.

This method can be a catalyst, preferably in the presence of a solvent, nitriding the above-mentioned one-shot I into the α, Ω-diamine basin H2N-CH2- (CH2) n-CH2-NH2 II of the following general formula II 11As defined above. Particularly preferred diamines II are η, 2, 3, 4, 5 or 6.

V. Explanation of the invention (7) ^--especially 4 '-4-diaminobutane, 5-diaminopentane, 16-diaminohexane ("hexamethylenediamine" ), The "diaminoheptane 'and the plant 8-diaminooctane' is the best 1,6-diaminohexane.

If the reaction is carried out in suspension, the temperature is generally selected from 60 to 2000. Within the range of 0, it is preferably selected from the range of 60 to 80, and particularly preferably selected from the range of 70 to 130. The pressure is generally selected from the range of 2 to 30 Mpa, preferably from the range of 3 to 30 Mpa, and particularly preferably selected from the range of 4 to 20 Mpa. The retention time is mainly determined by the desired yield and selectivity of the complete conversion; generally, the retention time is selected to obtain the maximum yield at the full conversion, for example, in the range of 50 to 3,000 minutes, preferably 70 to 2 The solvent of the D suspension method in the range of 0 minutes is preferably selected from the group consisting of ammonia, amines, diamines, and diamines with up to 6 anaerobic atoms, such as tris (methyl) amine, triethylamine, tripropylamine , And tributylamine, or alcohol, especially methanol and ethanol, especially ammonia. The concentration of the dinitrile is advantageously selected from the range of 10 to 90% by weight, preferably from 30 to "80" by weight, particularly preferably from 40 to 70% by weight, based on the sum of the two eyes and the solvent. Tablets generally choose the amount of catalyst so that the amount of catalyst is within the range of 1 to 50% by weight, preferably within the range of 5 to 20% by weight. Suspension hydrogenation is generally available in the liquid phase based on the amount of diazepam used. Batch by batch, or preferably continuous ^ ~ Hydrogenation can also be performed batchwise or continuously in a fixed bed reactor in drops ^: by direct pass or by product circulation, in this case, the degree of -3 on the square is 7 0 to 20 0. (: In the range, preferably in the range of 80 to 50 °, generally choose a temperature in the range of 2 to 40 Mpa, preferably in the range of 3 to 30 Mpa: Li Yi Jia in the presence of a solvent, preferably Ammonia, amine, diamine, etc. Gasification has less than 1 to 6

5. Description of the invention (8) Triamines of carbon atoms, such as trimethylamine, triethylamine, tripropylamine, and tributylamine 1 or alcohols, preferably methanol and ethanol, particularly preferably ammonia. In a preferred embodiment, the ammonia content is in the range of 1 to 10 grams per gram of adiponitrile, and preferably in the range of 2 to 6 grams. In this specific embodiment, it is preferred to use the catalyst space velocity in the range of 0.1 to 2.0 kg, preferably 0.3 to 1.5 kg in the range of binocular / liter X hours. The residence time can be varied in a specific way to adjust the conversion rate. The hydrogenation can be carried out in a conventional hydrogenation reactor.

C α, Ω-diamine hydrogenation to form α, Ω-diamine is known to form by-product α, Ω-amine. The method of the present invention can keep the amount of the amino nitrile to less than 2000 ppm, preferably less than 1000 ppm, and particularly preferably less than 500 ppm, based on diamine. The hydrogenation of hexamethylene diacetate as α Ω-dipermium gives the following and solvent mixtures, which mainly contain hexamethylene diamine, especially 6-amino hexamethylene diamine, hexamethyleneimine, and 2-aminofluorenyl ring Amylamine, 1,2-diaminocyclohexane, tetrahydroazaweed, and hexahexamethylenetriamine impurities. Purification of the crude hexamethylenediamine obtained after removal of the solvent is generally preferably carried out by distillation. α, Ω-diamine is an important starting compound for the manufacture of nylon-6,6. In the example:

ADN = hexamethylene diamine ACN = 6 -amino hexamethylene diamine HMD = hexamethylene diamine DCH = 1, 2-diamine cyclohexane AMCPA = 2 _ amino fluorenyl cyclopentylamine page 13 5. Description of the invention (9) '~~' BHMTA = Bishexamethylenetriamine = Diamino-2_cyanocyclopentanidine 1HA = Tetrahydroazaweed HMI = Hexamethyleneimine Obtained by quantitative gas chromatography. Example 1 a) Catalyst preparation The catalyst was prepared from magnetite used in magnetite under nitrogen; 4 ° C was heated for 6 hours to prepare. . Second look at J ί listed as: 72% weight Fe. .07 " Amount A. B. 0.03% reset € 8, 0. 4% center of gravity, 〇11. / Click · ®. ·

Ti, the rest is oxygen. g ο-m weight Si, 0.01% by weight " The cooled melting block is crushed in a collar crusher, and the particle size is separated by 5_3. The oxidation catalyst is cooled to room temperature at 45 (rc reduction 丄 / 1) in a 2 / ~ stream, and the catalyst is pure with a stream of N2 / air (with 1% air in nitrogen for 24 hours). At 45 ° C.

b) AND hydrogenation to HMD, two series of connected tubular reactors (total length of 4.5 m, d = 6 mm) were charged in 1 2 2 ml (240 g) prepared according to Example 1 a) Catalyst (size = 1.5 to 3 mm in size), and then reduced at 200 liters / h under a large (._ pressure) hydrogen pressure. For this purpose, the temperature was raised from 700c to "^ yi The calendar "small 4 'and then maintained at 3 40 ° C 7 2 hours. After the temperature was reduced, the reactor was charged with 74 ml / hour ADN (catalyst space velocity 0.5 kg ADN / liter catalyst X hours), 36 5 ml / Hour M3, and 200 standard liters / hour H2

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Page 15 387872 V. Description of the invention (11) Page 16) — »L / λ π ° 250 pressure (bar) 〇lyi 1 catalyst space velocity (kg ADL / liter catalyst X hours) >» · > ο ADN Conversion rate (%) 98.9 HMD yield (%) 1_ Ί 200 [ppm / HMD based] | 'ACN! 1_ 〇 \ ICCP AMCPA 1 1100 1 DCH 1! 1_ 〇THA

./IV

Claims (1)

387872 VI. Patent application iif 1. A method for preparing aliphatic α, Ω-diamine by hydrogenating aliphatic α, Ω-dinitrile in the presence of a catalyst, including the use of a hydrogenation catalyst (a) iron containing the following, or Iron-based compounds, or mixtures thereof, (b) 0.001 to 0.3% by weight based on (a), based on 2, 3, 4 or 5 promoters selected from the group consisting of: Ming, broken, wrong, Qin, and Xun , And (c) 0 to 0.3% by weight based on (a), compounds based on metal test and / or soil test metal. 2. The method according to item 1 of the scope of patent application, wherein the catalyst has a BET surface area of 3 to 20 square meters / gram, a total pore volume of 0.05 to 0.2 milliliter / gram, and an average pore diameter of 0.03 to 0. 1 micron, and 0.01-0.1 micron pore volume fraction is in the range of 50 to 70%. 3. The method according to item 1 or 2 of the scope of patent application, wherein the catalyst is reduced from magnetite and then obtained with or without purification. 4. The method according to item 1 or 2 of the scope of the patent application, wherein the accelerator based on 4 Lu, Chong, and Qin is used. 5. The method according to item 1 or 2 of the patent application scope, wherein a magnesium and / or calcium based accelerator (c) is used. 6. The method according to item 1 or 2 of the patent application scope, wherein the catalyst is Page 17 387872 VI. Scope of patent application The corresponding aliphatic 0:, Ω-amino group by-products of the family < 2, Ω-diamine less than 2000 ppm. · 10. The method according to item 1 or 2 of the scope of the patent application, wherein the aliphatic α, Ω-dione used is composed of α, Ω-diene with less than two carbon atoms in the presence of a catalyst Obtained by hydrocyanation. 1 1. The method according to item 10 of the scope of patent application, wherein the weight of the phosphorus compound in the α, Ω-diphthalene is partially reduced. 1 2. The method according to item 11 of the scope of the patent application, wherein after the amount of the phosphorus compound is reduced, the weight of the lin compound is less than 5 1 on a scale basis. 3. According to the scope of the patent application, either 1 1 or 1 2 The method of item, wherein after the amount of the phosphorus compound is reduced, the weight portion of the compound is filled in less than 1 ppm in terms of lin, based on α, Ω-binocular. 14. A catalyst substance for preparing an aliphatic α, fluorene-diamine from an aliphatic α, Ω-dieye, comprising (a) iron, or an iron-based compound, or a mixture thereof, (b) based on (a) 0.001 to 0.3% by weight based on 2, 3, 4 or 5 promoters selected from the group consisting of: Shao, hard, tungsten, titanium, and rhenium, and (c) 0 to 0.3% by weight based on (a), Based on metal test and / or earth test compound. Page 18