Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
  • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles

Definitions

• Secondary aliphatic amines in particular the so-called fatty amines with long carbon chains, are today produced in large-scale industrial processes essentially in two different ways by two basic procedures, namely by the hydrogenation of corresponding nitriles or by the so-called aminolysis or ammonolysis, i.e. the reaction of fatty alcohols with ammonia or primary amines in the presence of hydrogen.
• Such processes for the production of secondary amines from nitriles are known, for example, from DT-PS 963 518, DT-PS 1 280 243, DT-PS 1 941 290, US-PS 2 781 399, and US-PS 2 784 232 and GB-PS 836 364.
• a process is known from DT-AS 1 219 493 according to which tertiary amines having 6 to 26 carbon atoms in each aliphatic group are prepared from mixtures of the corresponding aliphatic alcohols with corresponding nitriles, in which at temperatures between 160 and 280 ° C and at a pressure between 7 and 14 bar in the presence of hydrogenation catalysts, hydrogen is passed through the starting materials present in the liquid phase. Water vapor or ammonia formed during the reaction is removed from the reaction by the excess hydrogen passed through. Under these conditions, primary and secondary amines can practically only be obtained in minor amounts as by-products.
• nitrile molar ratio 90:10 to 10:90 with at least 2 mol of hydrogen . brings intimate contact per mole of nitrile, an ammonia concentration of 3 to 75 vol .-% being maintained in the reaction gas during the entire reaction time.
• the starting materials for the process according to the invention are, on the one hand, aliphatic alcohols of the formula R 1 OH, in which R 1 is an alkyl radical or a mono- or polyethylenically unsaturated hydrocarbon radical which has a total of 8 to 26 carbon atoms.
• R 1 is an alkyl radical or a mono- or polyethylenically unsaturated hydrocarbon radical which has a total of 8 to 26 carbon atoms.
• Such alcohols can have one or more chain branches in the chain in the form of secondary or tertiary C atoms, but they have at most one branch in the ⁇ position to the OH group, that is to say they are primary or secondary alcohols.
• Examples include: n-octyl alcohol, 2-ethylhexanol, isooctyl alcohol, isononyl alcohol, lauryl alcohol, isotridecyl alcohol, oleyl alcohol, cetyl alcohol and stearyl alcohol.
• alcohols or mixtures of alcohols which are formed in the hydrogenation of natural fatty acids or fatty acid esters, such as, for example, tallow fatty alcohol or palm kernel fatty alcohols. These include also the mono- to poly-unsaturated alcohols that are formed during the hydrogenation of the poly-unsaturated fatty acid esters of trans- and rapeseed oil fatty acids.
• the inexpensive primary alcohols with up to 24 carbon atoms which are obtained through the ethylene build-up according to the Ziegler process.
• More or less branched alcohols such as those produced by straight-chain or branched, middle or terminal unsaturated olefins by oxosynthesis, or the isooctadecyl alcohol accessible from isononyl aldehyde can also be used as starting alcohols.
• Suitable secondary alcohols are, for example, those which are obtainable by the known processes for the direct oxidation of straight-chain and branched paraffins in the presence of boric acid.
• the starting alcohols can be in the form of any mixtures.
• Straight-chain and branched primary alcohols which are saturated or unsaturated with 1 to 2 ethylenic double bonds and which have 14 to 22, in particular 16 to 18, carbon atoms are preferred.
• Suitable starting alcohols in the process according to the invention are also ether alcohols such as those formed by oxethylation and / or oxpropylation of primary and secondary alcohols.
• the radical R assumes the meaning R 2 (OX) m -.
• the units can be units derived exclusively from ethylene oxide or propylene oxide, or they can also be mixtures of such units, in statistical distribution or in the form of blocks.
• m means the average; Degree of oxalkylation. Therefore, m can be both an integer and a fractional number, which is between 1 and 20, preferably between 1 and 8 and in particular between 1 and 3 for the starting alcohol component of the process according to the invention.
• R 2 can be a straight-chain or branched alkyl, alkenyl or polyethylenically unsaturated hydrocarbon radical having 1 to 26, preferably 8 to 22, carbon atoms, but with the proviso that the molecular weight of the entire radical R 2 (OX) m - m in- d should be minutely 130, since only such radicals under J 'the reaction conditions of the inventive method result in a sufficiently low vapor pressure of the alcohol, which prevents the starting alcohol is discharged with the reaction water from the process.
• the ether alcohols mentioned can also be used in a mixture with the above-mentioned straight-chain or branched, saturated or unsaturated, primary or secondary alcohols.
• the second reaction component in the process according to the invention are nitriles of the formula in which the radical R 3 can likewise be an alkyl radical or a mono- or polyethylenically unsaturated hydrocarbon radical, but here, in contrast to the starting alcohols, a tertiary carbon atom can also be present in the a-position. Otherwise, the same applies to the chain branches in R 3 as was said for the radicals R 1 of the starting alcohols. These radicals R 3 have 8 to 26 carbon atoms. Straight-chain and branched saturated nitriles or those with up to 3 ethylenic double bonds which have 14 to 22, in particular 16 to 18, carbon atoms are preferred.
• the starting nitriles can also be used in the form of any mixtures within the limits mentioned.
• nitriles required as starting components in the process according to the invention are prepared from the same-chain carboxylic acids by known processes by reaction with ammonia under dehydrating conditions. Such nitriles are also accessible by the so-called ammonoxidation of hydrocarbons or by the nitrilization of alcohols with ammonia, which is preferably carried out on iron contacts.
• Ether nitriles are also suitable as starting nitriles, whereby the radical R 3 then has the meaning R 4 - (OX) -O (CH2) -, n wherein R 4 is a straight-chain or branched alkyl, alkenyl or polyethylenically unsaturated hydrocarbon radical having 1 to 26 C atoms, preferably 8 can be up to 22 carbon atoms.
• R 4 is a straight-chain or branched alkyl, alkenyl or polyethylenically unsaturated hydrocarbon radical having 1 to 26 C atoms, preferably 8 can be up to 22 carbon atoms.
• (OX) here are also units which are formed by oxyalkylation with ethylene oxide and / or propylene oxide and which in turn, if both oxyalkylate radicals are present, can be randomly distributed or in the form of block copolymers.
• the degree of oxalkylation n can assume the same values as m in the starting ether alcohols, but it can also become zero in the case of ether nitriles.
• the index p can be 1 or 3.
• the requirement also applies to the ether nitriles that the entire radical R 4 - (OX) n -O (CH 2 ) p- should have at least the molecular weight 130.
• nitriles and / or ether nitriles which can be used within the abovementioned limits can also be present in the form of mixtures.
• the starting alcohols and the starting nitriles are in the liquid phase during the reaction.
• the implementation in the context of the method according to the invention takes place under depressurized conditions, that is to say practically under normal pressure.
• the temperature during the reaction according to the process according to the invention should be between approximately 120 and approximately 260 ° C., preference is given to working in a temperature range between approximately 180 and approximately 260 ° C. in order to achieve economical reaction rates. However, a noticeable conversion to the desired secondary amines is also taking place in the latter area at the temperatures below from 120 ° C., which may optionally be deliberately run slowly.
• Such contacts are required as catalysts which simultaneously have a hydrogenation and a dehydrogenation function.
• These are preferably nickel contacts, which can be in the form of the active Raney nickel types as well as in grain or powder form with or without a carrier material.
• the corresponding cobalt contacts or nickel-cobalt or nickel-cobalt-copper mixed contacts are also suitable, as are copper chromite catalysts, which can optionally be provided with additives of copper oxide, alkali or alkaline earth metals, such as, in particular, barium.
• the nickel and cobalt catalysts of the most varied types with and without additions of other metals and with supports and activators are particularly suitable for the process according to the invention.
• Manganese, iron oxide, zinc oxide, aluminum silicates, aluminum oxide and Si0 2 in the form of diatomaceous earth or as a blown synthesis product may be mentioned as additives and carriers.
• the nickel contacts deserve priority.
• the preferred temperature range of the process according to the invention depends to a certain extent on the type of catalyst.
• the temperature range from 180 to 200 ° C has proven to be particularly favorable. These temperatures can be easily adjusted, in particular in the case of high-boiling starting alcohols and starting nitriles from about 12 carbon atoms.
• the optimal temperature cannot be set immediately from around 180 ° C.
• the reaction is started at 120 ° C. and a relatively small amount of the reaction gas is first introduced into the nitrile-alcohol mixture. At this temperature, the conversion into high-boiling secondary amines or their precursors begins. As the reaction progresses, both the temperature and the amount of gas can then be slowly increased.
• the optimal reaction temperature is around 230 to 250 ° C.
• nitrile-alcohol mixtures from around 15 to 16 carbon atoms or those with approximately the same boiling points or corresponding vapor pressures can be set directly to the reaction temperature without having to go through a slow heating-up period.
• the amount of catalyst for the process according to the invention depends not only on the type of contact but also on the chosen reaction temperature. It is within limits within the method according to the invention between 1 and 6% by weight, based on the weight of the reactants and calculated on active metal or metal oxide.
• the required amount of contact with Raney nickel under otherwise identical conditions was 5% by weight at 180 ° C, 2% by weight at 200 ° C and at 210 ° C 1% by weight. At 210 ° C there were minor side reactions.
• the reaction mixture has to be offered at least two moles of hydrogen per mole of nitrile; an excess of hydrogen, which can be of any size, does not interfere.
• the amount of hydrogen that may be required for the hydrogenation of ethylenically unsaturated double bonds of the starting nitriles or alcohols must also be taken into account. Hydrogen must be offered to the reaction mixture from the start, since otherwise undesirable side reactions occur.
• the hydrogen concentration present in the reaction gas is calculated from the ammonia concentration mentioned below as a difference against 100%.
• the reaction gas is understood to be only the sum of hydrogen and ammonia.
• ammonia is also present in the reaction gas in addition to hydrogen during the entire reaction time. Care must therefore be taken to ensure that the ammonia does not escape in an uncontrolled manner, since an ammonia deficit significantly reduces the yield of secondary amine.
• the ammonia concentration can be between 3 and 75 vol .-% in the reaction gas. It can be both internal half of this range are kept constant during the entire reaction time and fluctuate within this limit. The limits mentioned can, in particular, be exceeded for a short time, and may even be slightly below.
• ammonia concentration be controlled so that it is essentially maintained within these limits during the reaction period. If the limit of the ammonia concentration in the reaction gas is undershot, an increase must be made; if it is exceeded, the ammonia concentration must be lowered. This applies both to ammonia components that are supplied or removed from the outside, and to those that arise from the reaction partners themselves.
• the proportion of the reactants alcohol and nitrile can vary within wide limits in the process according to the invention, up to a molar ratio of alcohol: nitrile between 90:10 and 10:90.
• a molar ratio of alcohol: nitrile between 70:30 and 30:70 is preferred, and in particular the reaction between equimolar proportions of both partners, with an molar ratio of alcohol: nitrile between 60 being below equimolar with regard to the technical circumstances (for example the purity and uniformity of the starting materials) : 40 and 40: 60 should be understood.
• the ammonia concentration should be between approximately 3 and 60% by volume and preferably between 3 and 50% by volume.
• the ammonia concentration should remain more in the lower part of the range in the case of a large excess of nitrile and more in the upper part of the range in the case of a large excess of alcohol. In the latter case, there is also the requirement that a total of at least 1/2 mole of ammonia should be offered per mole of excess alcohol.
• the gas mixture should The rate at which the reaction gas, possibly including inert gas, passes through the liquid phase or comes into intimate contact with it moves between 200 and 600 l of gas per kg of reactant mixture per hour. These limits are not absolutely critical, but the reaction is slower at lower gas velocities, about 50 to 100 liters per kg and hour. On the other hand, gas quantities above 600 l per kg and hour only offer advantages if it is ensured that the larger quantities can also be optimally distributed in the liquid phase. Above 1000 liters per kg and hour, the amount of gas is mainly limited in terms of technical feasibility and economy.
• the intimate contact between liquid, gas and catalyst required for the reaction is usually established by the gas being introduced or circulated directly with the suspended contact, with very good stirring or pumping around the liquid phase. Jet reactors are particularly advantageous for such a circulation.
• the liquid reaction material is intimately mixed with the catalyst and the reactive gases in a jet nozzle, as a result of which a particularly rapid reaction takes place.
• the jet nozzle simultaneously circulates the gas phase and separates the water of reaction outside the boiler.
• the highest possible amount of gas is also of great importance for the quick and easy discharge of the water of reaction formed.
• the reaction gas that is to say the mixture of hydrogen and ammonia
• the reaction gas can be diluted with portions of inert gases such as nitrogen or methane.
• Inert gases can be present in proportions of 0 to 50% by volume in the gas mixture in addition to the reactive gases hydrogen and ammonia. Such gases reduce the partial pressures of hydrogen and ammonia, but on the other hand they promote the important discharge of the water of reaction.
• the reaction can take place according to the so-called open ' also the so-called closed driving style can be carried out.
• the open procedure consists in that, with good stirring, hydrogen is passed through the reaction vessel charged with the reaction mixture of alcohol and nitrile, which at the same time contains the catalyst, at the required reaction temperature, where necessary the amount of ammonia required to maintain the ammonia concentration in the reaction mixture is fed with.
• the outlet of the apparatus is openly connected to the atmosphere via a descending cooler, which advantageously contains a template for the absorption of the water of reaction.
• the excess reaction gases leave the apparatus via an exhaust pipe.
• the closed mode of operation which can also be referred to as gas cycle mode, is the preferred embodiment of the method according to the invention.
• gas cycle mode In terms of equipment, it differs from the so-called open mode of operation in that hydrogen and ammonia are circulated through a circulation pump by means of a highly effective condenser after the water of reaction has been condensed out.
• the used hydrogen and ammonia are fed into the equipment.
• the closed mode of operation can therefore be used with the same high yields of secondary amines with significantly smaller amounts of the two gases.
• the ammonia loss can still be kept particularly low if the separated water of reaction is advantageously set to about 90 ° C. and the exhaust gases can condense via a reflux condenser. Instead of an approximately 10% by weight ammonia water, a 1 to 3% by weight ammonia solution is obtained with this measure.
• the apparatus for the cycle gas mode of operation of the method according to the invention also has a switchable device, with the aid of which excess or ammonia present in the cycle gas can be removed completely or partially.
• the device for regulating ammonia is advantageously located in the bypass of the gas circuit of the apparatus. It comes into operation as soon as the desired ammonia concentration is exceeded.
• Said device can be, for example, a washing tower or stirred tank filled with liquid absorbent, but also an adsorption tower filled with solid adsorbents.
• Water or aqueous sulfuric acid for example, can serve as the adsorbent for ammonia in the device mentioned.
• Concentrated sulfuric acid can also be used, which is injected in doses at a certain point in the gas circulation if necessary.
• the ammonia concentration in the reaction gas is monitored, for example, with the aid of an infrared analysis device, a process chromatograph or also with the aid of another continuous analysis device which supplies analysis values according to chemical or physical methods.
• the analyzer used can advantageously regulate the supply and discharge of ammonia automatically.
• the ammonia concentration can be adjusted by means of a cooling unit which can both remove ammonia from the circuit and also release ammonia to it.
• a cooling unit which can both remove ammonia from the circuit and also release ammonia to it.
• Such a unit can be installed in both the main circuit and the secondary circuit.
• Unsaturated nitriles and alcohols can also be used in the process according to the invention.
• the unsaturated alkyl chains can contain both one and more double bonds. Examples include: oleyl alcohols with iodine numbers from 50 to 95, tallow fatty nitrile with an iodine number of about 50 "and the nitriles of tranoleic and rapeseed oil fatty acids with iodine numbers greater than 100, furthermore oleyl nitrile and soybean oil nitrile.
• the process can be controlled so that both saturated as well as the corresponding unsaturated or partially unsaturated secondary amines are obtained
• the double bonds are best suited to copper-chromium catalysts.
• Unsaturated or partially unsaturated secondary amines can also be obtained from unsaturated nitriles and alcohols with nickel contacts.
• a reaction gas is particularly advantageous which, in addition to hydrogen, contains about 10 to 60, preferably 20 to 50,% by volume of ammonia.
• Saturated secondary amines from unsaturated starting components are most advantageously obtained when the ammonia content of the reaction gas is in the lower range of the specified limits and when the reaction gas is replaced by pure hydrogen after the formation of the secondary amine has ended. If necessary, the temperature can be increased and the amount of gas increased.
• the process according to the invention for the formation of the secondary amine usually takes 1.5 to 4, preferably 2 to 3 hours. In extreme cases (with a high iodine number) approximately the same time is again required for the complete hydrogenation of existing double bonds.
• the post-hydrogenation phase can be shortened if the pressure is increased, for example at 4 to 10 bar.
• the yield of amines obtained by the process according to the invention is about 90 to 99%, in most cases it is more than .95%, that is to say almost quantitative.
• the difference consists of non-amine constituents, in particular small amounts of degradation products of the starting alcohols and nitriles, as well as impurities in the starting materials of technical quality.
• the proportion of the desired secondary amines is 80 to 95 mol%, in most cases over 90 mol%, based on the total yield of amines equal to 100 mol%.
• the rest are primary and tertiary amines, with the primary amines often being completely absent.
• the color q uality of the obtained secondary amines is very good. Iodine color numbers of 0.2 to 2 units are certainly obtained (iodine color numbers according to DIN standard 6162).
• the secondary amines obtained generally do not require a special purification process by a distillation or absorption process for further processing.
• the secondary amines which can be prepared by the process according to the invention are above all valuable intermediates. They are preferably used for the production of plasticizers for textiles, components for organophilic ammonium bentonites and microbiocides, especially for combating bacteria, fungi and algae. They also serve for the production of antistatic agents, conditioning and preparation aids, for hair cosmetics and for synthetic fibers. Secondary amines with a total of 20 C atoms several times can also be used for the liquid extraction of metals, such as tungsten, in strongly acidic solutions.
• the secondary amines which can be prepared by the process according to the invention can be converted into symmetrical secondary amines (both radicals consist of a pure hydrocarbon radical or of a hydrocarbon radical containing ethoxy and / or propoxy groups) and unsymmetrical secondary amines (a radical consists of a pure hydrocarbon residue and the other of an ethoxy and / or propoxy group containing hydrocarbon residue).
• the invention therefore also relates to secondary amines of the formula I. wherein R 1 , R 2 and X have the meaning given and y is a number from 1 to 20.
• R 1 and R 2 are branched or preferably straight-chain alkyl radicals, in particular R 1 is an alkyl radical with 8 to 22 carbon atoms and R 2 is an alkyl radical with 4 to 22 C atoms, and X and y have the aforementioned meaning.
• R 1 and R 2 are branched or preferably straight-chain alkyl radicals, in particular R 1 is an alkyl radical with 8 to 22 carbon atoms and R 2 is an alkyl radical with 4 to 22 C atoms, and X and y have the aforementioned meaning.
• the secondary amines of the formula I according to the invention are preferably used to prepare the corresponding quaternary ammonium salts which have valuable properties as textile auxiliaries.
• the apparatus consists of a reaction flask equipped with a gas inlet, a stirrer, a contact thermometer and a Raschig column that can be heated to 90 ° C.
• a water separator is installed on this column, which can also be heated up to 90 ° C if necessary, if the concentration of the dissolved ammonia in the separated reaction water is to be kept as low as possible.
• This is followed by an absorption vessel with 1-normal sulfuric acid, in which ammonia that has been removed can be recorded by titrimetry.
• the reaction gas in the apparatus is circulated through a circulation pump. Hydrogen required for the reaction is introduced into the circuit in such a way that an overpressure of up to 0.1 bar can prevail in the apparatus.
• Exhaust gas can be taken off at the outlet of the apparatus.
• the H 2 S0 4 absorption vessel can be switched in such a way that the circulating gas can be passed over it both in full and in the bypass of the circuit. It is also possible to carry out the absorption of the ammonia outside the circulating gas in the exhaust gas in an H 2 S0 4 absorption vessel.
• the batch After heating to 200 ° C., the batch is run at this temperature for 3 hours, and 52.6 l of hydrogen are fed in during this time. By removing 2 l of exhaust gas, the ammonia concentration in the cycle gas is kept in the range between 3 and 25% by volume.
• the product is allowed to cool to 100 ° C. in a circulating gas stream and the apparatus is flushed with nitrogen. A total of 0.131 moles of ammonia are collected in the sulfuric acid receiver in the exhaust line.
• the water of reaction formed (16.3 g) contains a further 0.023 mol of ammonia.
• the contents of the flask are then sucked off at approx. 80 ° C through a diatomaceous earth filter through a suction filter. There are 96.3 wt .-% total yield of amine with an amine number of 17.40. It is composed of 92.1 mol% of secondary amine, the rest is tertiary amine, primary amine was not found.
• a circulating gas amount of 500 1 circulating gas / kg. Set hour and the apparatus heated to 180 ° C. At this temperature, driving is carried out for 5 1/2 hours, during which time 58 l of hydrogen are introduced.
• the reaction temperature of 180 ° C. is reached, the circulating gas contains 6% by volume of ammonia, 20% by volume after 1/2 hour and 34% by volume after 1 hour.
• Exhaust gas is now taken off via the H 2 S0 4 absorption part in the exhaust line, as a result of which the ammonia level is kept at 35% by volume.
• reaction time 35% by volume of ammonia are measured, after 4 and 5 hours 30.5% and 25% by volume, respectively.
• the cycle gas still contains 15% by volume of ammonia.
• 13.6 l of exhaust gas containing 0.181 mol of ammonia have been continuously removed from the apparatus.
• 6.9 g of water of reaction are also obtained, containing a further 0.061 mol of ammonia.
• a further 0.029 mol of NH 3 are collected when the apparatus is rinsed.
• the total amine yield is 95.3% by weight with an amine number of 31.85. This contains 3.1 mol% primary amine, 92.2 mol% secondary Amine and 4.7 mol% tertiary amine.
• the circulating gas volume is increased to 500 l / kg. Hour, it is heated to 180 ° C. and the batch is run at this temperature for 4 1/2 hours, during which time 36.4 l of hydrogen are added.
• 5% by volume of ammonia are contained in the cycle gas, 20% by volume after 1 hour and 30% by volume after 3 hours. Exhaust gas is not removed.
• the ammonia concentration then drops to 18% by volume at 3 hours and to 6% by volume at 4 hours.
• 3% by volume of ammonia are measured. 11.3 g of water of reaction are formed which contain 0.065 mol of ammonia, and a further 0.011 mol of ammonia are collected when the apparatus is rinsed.
• the total amine yield is 97.4% by weight with an amine number of 31.47. Of these, 0.1 mol% are primary amine, 91.0'Mol% secondary didecylamine and 8.9 Mol% tertiary tridecylamine.
• the circulating gas volume is 500 l / kg. Hour, the reaction temperature 180 ° C and the reaction time 5 1/2 hours. During this time, 32.9 liters of hydrogen are fed in continuously. After heating, the circulating gas initially contains 7% by volume of ammonia, after 1/2 hour 25% by volume, after 1 hour 33% by volume and after 2 hours 35% by volume of ammonia, without additional ammonia being added . The ammonia concentration in the cycle gas then drops again and is still 3% by volume at the end of the reaction time. 13.0 g of water of reaction are obtained, containing a further 0.034 mol of ammonia. The crude product obtained after removal of the contact contains 95.8% by weight of total amine with an amine number from 30.2.
• the determination shows that it contains 84.0 mol% of secondary amine, 16.0 mol% of tertiary amine and no primary amine, with sec. Amine (bp. 13 212 - 218 ° C) all 3 possible species can be detected by gas chromatography.
• the circulating gas volume is 500 l / kg. Hour, the reaction temperature 190 ° C and the reaction time 6 1/2 hours.
• the apparatus After the apparatus has been filled with hydrogen after nitrogen flushing, it is first heated to 140 ° C. and then gaseous ammonia is introduced in a proportion of 10% of the circulating gas volume. A total of 24.1 liters of hydrogen are run in during the entire reaction time, that is to say when 190 ° C. is reached. Ammonia accumulates rapidly in the circuit. Immediately after the reaction temperature has been reached, the ammonia concentration is 27% by volume, 60% by volume after 1/2 hour of reaction time and 67% by volume after 1 hour.
• the circulating gas volume is 500 1 / kg. Hour. After filling the apparatus with hydrogen, the mixture is heated to 200 ° C. with vigorous stirring. At a temperature of 140 ° C, a proportion of 10% of the circulating gas volume of gaseous ammonia is brought in.
• the reaction time is 2 1/2 hours at a temperature of 200 ° C, during which 22.1 l of hydrogen are continuously fed into the circuit.
• the ammonia concentration is 42% by volume at the beginning of the reaction, it drops to 33% by volume after 1/2 hour, to 18% by volume after 1 hour and to 11% by volume at the end of the reaction. During this time, 7.2 g of water containing 0.005 mol of ammonia are collected in the water separator, which is heated to 90 ° C.
• the circulating gas volume is 500 l / kg. Hour, the reaction temperature 200 ° C and the reaction time 5 1/2 hours.
• about 10% of the circulating gas volume of gaseous ammonia is again introduced into the circuit at 140 ° C., and hydrogen is also fed continuously.
• 40% by volume are contained in the cycle gas, 24% by volume after 1/2 hour, 11% by volume after 1 hour and less than 4% by volume of ammonia at the end of the reaction.
• the circulating gas volume is 500 l / kg. Hour, the reaction time at 200 ° C 2 1/2 hours. During this time, 32.2 liters of hydrogen are fed into the circuit. Ammonia is rapidly enriched in the circuit, so part of the circulating gas in the secondary circuit is passed through dilute H 2 SO 4 in order to keep the ammonia concentration in the circulating gas between 35 and 50% by volume. 0.102 mol of ammonia are determined in the sulfuric acid, and a further 0.009 mol of ammonia are contained in the water of reaction (6.5 g).
• the circulating gas volume is 500 l / kg. Hour, the reaction temperature is 200 ° C.
• the ammonia concentration in the cycle gas is between 30 and 40% by volume, and then drops to 8% by volume after the end of the reaction time after 2 1/2 hours. After this time, a total amine results in a yield of 97.1% by weight with an iodine number 10 and an amine number 19.07.
• This total amine contains 3.9 mol% primary, 91.7 mol% secondary and 4.5 mol% tertiary amine.
• the cycle gas is then circulated at 200 ° C. for a further hour, passing through dilute sulfuric acid to remove the ammonia. During this time another 1.4 l of hydrogen are added.
• the result is an amine with a residual iodine number of 3 and an amine number of 18.92, which contains 1.3 mol% of primary, 93.3 mol% of secondary and 5.4 mol% of tertiary amine.
• a circulating gas circulation of 500 l / kg. Set hour and heated to 180 ° C with vigorous stirring.
• gaseous ammonia is introduced into the circuit at a rate of 10% of the circulating gas volume.
• the reaction time is 8 hours, during which 22.3 l of hydrogen are run in.
• the ammonia concentration in the cycle gas is 13% by volume, 35% by volume after 2.5 hours, 21% by volume after 5 hours and 5% by volume at the end.
• a total amine results in a yield of 94.0% with an iodine number of 20 and an amine number of 17.97, 11.9 mol% of primary, 86.4 mol% of secondary and 1.8 mol% % consists of tertiary amine.
• ammonia is added in an amount of 10% of the circulating gas volume.
• 20.9 l of hydrogen are introduced during the reaction time.
• the ammonia concentration increases slowly, it is 25% by volume after 4.5 hours, and then slowly decreases again to 13% by volume at the end of the reaction.
• a total amine is obtained with a yield of 88.5% by weight, an iodine number of 27 and an amine number of 16.38. This consists of 10 mol% of primary, 82.3 mol% of secondary and 7.7 mol% of tertiary amine.
• Example 6 octane nitrile and tetraethylene glycol mono-n-butyl ether are reacted in the circulating apparatus at 200 ° C. for 8 hours.
• the circulating gas volume is 500 1 / kg. Hour.
• the ammonia level in the cycle gas is 46% by volume at the beginning of the reaction and drops to 5% by volume.
• the fraction at a head temperature of 232 to 236 ° C contains, according to gas chromatographic analysis, 95% by weight of the compound C 8 H 17 -NH- (CH 2 CH 20 ) 4 -nC 4 H 9 .
• the gas chromatographic analysis was carried out in a 1.5 m high column of 2 mm diameter, provided with a filling of 5% by weight "Silicon Fluid QF 1 " on "Chrarnson3 G-AW-DMCS" (available from Merck AG, Darmstadt); Carrier gas flow: 20 ml / min nitrogen; Temperature progression: 80 to 250 ° C with 2 ° C per minute gradient; Sample volume: 0.2 ⁇ l.

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  • 1978-07-24 JP JP8952278A patent/JPS5424804A/ja active Granted
  • 1978-07-24 SU SU782637650A patent/SU755192A3/ru active
  • 1978-07-24 ZA ZA00784190A patent/ZA784190B/xx unknown
  • 1978-07-24 AU AU38268/78A patent/AU3826878A/en active Pending
  • 1978-07-24 AT AT534078A patent/AT361453B/de not_active IP Right Cessation
  • 1978-07-24 BR BR7804746A patent/BR7804746A/pt unknown
  • 1978-07-24 PT PT68343A patent/PT68343A/pt unknown
  • 1978-07-24 CA CA308,006A patent/CA1114838A/fr not_active Expired
  • 1978-07-24 AR AR273046A patent/AR222801A1/es active

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