CN1111153C - Selective fatty amine preparing method - Google Patents
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- CN1111153C CN1111153C CN 99125946 CN99125946A CN1111153C CN 1111153 C CN1111153 C CN 1111153C CN 99125946 CN99125946 CN 99125946 CN 99125946 A CN99125946 A CN 99125946A CN 1111153 C CN1111153 C CN 1111153C
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- 150000001412 amines Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- -1 aliphatic amines Chemical class 0.000 description 19
- 150000003512 tertiary amines Chemical class 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 7
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 1
- 229910020514 Co—Y Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种选择性制备脂肪胺的方法，是在可及时分离气相物流的反应器中，在加氢脱氢催化剂的活性温度下以及使醇原料和非目的脂肪胺产物保持液态的系统压力下，通入摩尔比为1∶1～12的由C2～C24脂肪醇和选自氨、一甲胺或二甲胺之一的物质组成的混合原料，在醇氢摩尔比为1∶1～20的范围内调节氢气量，将生成的目的产物单取代脂肪胺及时带离反应区域收集，并维持反应区域液面恒定。该方法在保证较高转化率和较低氨(胺)醇比的条件下，明显提高了单取代脂肪胺的选择性。A method for the selective preparation of fatty amines is carried out in a reactor capable of separating gaseous phase streams in time, at the active temperature of the hydrodehydrogenation catalyst and under the system pressure that keeps the alcohol feedstock and non-purpose fatty amine products in a liquid state. A mixed raw material composed of C 2 -C 24 fatty alcohol and a substance selected from ammonia, monomethylamine or dimethylamine with a molar ratio of 1:1~12, in the case where the molar ratio of alcohol to hydrogen is 1:1~20 Adjust the amount of hydrogen within a certain range, take the generated target product mono-substituted aliphatic amine away from the reaction area in time for collection, and keep the liquid level in the reaction area constant. The method obviously improves the selectivity of the monosubstituted aliphatic amine under the condition of ensuring a higher conversion rate and a lower ratio of ammonia (amine) to alcohol.
Description
The present invention relates to a process for the preparation of fatty amines.
In the industrial production of aliphatic amines, aliphatic alcohols, aldehydes or ketones are generally used as raw materials to react with ammonia, methylamine or dimethylamine in the presence of a hydrogenation dehydrogenation catalyst to produce aliphatic primary, secondary or tertiary amines. For example, primary, secondary and tertiary alkylamines can be formed starting from ammonia; methylamine is used as a raw material to generate methyl alkyl secondary amine, methyl dialkyl tertiary amine and trialkyl tertiary amine; dimethyl amine is used as raw material to produce dimethyl alkyl tertiary amine and methyl dialkyl tertiary amine. As can be seen from the above, ammonia, methylamine or dimethylamine are used as raw materials to react with alkyl-containing fatty alcohol, aldehyde and ketone compounds, so as to obtain alkyl mono-, di-and tri-substituted fatty amine products, and the three products have chemical thermodynamic equilibrium, that is, the reaction system does not only carry out amination reaction of alcohol, aldehyde and ketone, but also carries out disproportionation reaction of mono-, di-and tri-substituted fatty amines. In the case of ammonia and alcohol as starting materials, several disproportionation reactions can be represented as follows:
therefore, in the case of a catalyst and a process form, the ratio of the three types of aliphatic amines produced is limited by the chemical thermodynamic equilibrium, and a certain type of amine cannot be selectively produced. Although the selectivity of the mono-substituted aliphatic amine can be improved to a certain extent by improving the ammonia (amine) ratio, the increase is limited, and the recovery cost is increased due to the excessive use amount of ammonia. The prior art has been studied in a number of ways in order to increase the selectivity of certain amines.
US 4,251,465 changes the catalyst support, uses magnesium aluminate spinel to replace the commonly used gamma-alumina, impregnates metals such as copper, chromium, etc., reacts the dodecanol and dimethylamine, and under the same reaction conditions, the content of dimethyl dodecyl tertiary amine in the product is increased from 68.8% to 89.0%, but the used magnesium aluminate spinel is high in price and is not easy to obtain.
US 4,654,440 uses gamma-alumina as carrier, adjusts the formula of the dipping metal, uses the oxide of copper, antimony, manganese, tin and other metals as active component, carrieson the reaction of n-octyl alcohol and ammonia, under the reaction condition of 230 deg.C, the ratio of ammonia, hydrogen and alcohol is 20: 5: 1, the selectivity of n-octyl amine reaches 80%, but the conversion rate is lower, only 60%, and the consumption of ammonia is too large.
US 4,918,234 in C2～C4Alcohol is used as raw material, Co-Y molecular sieve and other shape-selective catalysts are used, the limitation of chemical equilibrium is broken, the selectivity of primary amine can reach 90% at most, basically no tertiary amine exists, but the conversion rate is lower, only 43%, and the method is only suitable for low-carbon alcohol (C)2～C4) Amination reaction of (a).
CN 1057831A changes the reaction process, adopts two-stage method to carry out reaction from C under normal pressure2～C9Fatty alcohol to prepare fatty amine. The main products of the first stage are nitrile and secondary amine, the fractions before the secondary amine are cut by distillation, the second stage reaction is carried out, the nitrile is converted into primary amine, the two-stage reaction is integrated, the selectivity of the primary amine is relatively high, for example, the selectivity of isooctylamine is 56%, the conversion rate is 94.6%, but the whole process flow is long, the operation is complex, and the selectivity of the primary amine is relatively high.
The invention aims to provide a method for selectively preparing alkyl monosubstituted aliphatic amine, which has simple process and mild process conditions, and improves the selectivity of the monosubstituted aliphatic amine under the condition of ensuring higher conversion rate and lower ammonia (amine) ratio.
The key point of the method is that by utilizing the rule that chemicalthermodynamic equilibrium exists among mono-substituted, di-substituted and tri-substituted fatty amine in a reaction product and the characteristic that the boiling point of the mono-substituted fatty amine is the lowest, the gasification amount of the mono-substituted fatty amine with the lowest boiling point is larger than that of the di-substituted and tri-substituted fatty amine (namely the concentration of the mono-substituted fatty amine in a gas product is larger than the equilibrium concentration of the mono-substituted fatty amine in the total product) by controlling the reaction condition, and the gaseous mono-substituted fatty amine leaves a reaction area in time, while the di-substituted and tri-substituted fatty amine is in a liquid state and remains in the reaction area for continuous reaction. And the gas phase material flow enters a gas-liquid separator after being condensed and cooled. The separated gas (hydrogen, ammonia, monomethylamine, dimethylamine, etc.) is circulated back to the reaction system, and the separated liquid is the target product with high concentration, which can meet the industrial requirement and can be further refined to obtain high-purity product.
The method for selectively preparing the mono-substituted aliphatic amine comprises the step of introducing C with the molar ratio of 1: 1-12 into a reactor capable of timely separating gas phase material flow under the activity temperature of a hydrogenation and dehydrogenation catalyst and the system pressure of keeping an alcohol raw material and a non-target aliphatic amine product in a liquid state2～C24The method comprises the following steps of adjusting the hydrogen amount of a mixed raw material consisting of aliphatic alcohol and one of ammonia, monomethylamine or dimethylamine within the range of the molar ratio of alcohol to hydrogen of 1: 1-20, carrying the generated target product mono-substituted aliphatic amine out of a reaction area and collecting the mono-substituted aliphatic amine, and maintaining the liquid level of the reaction area to be constant.
The method of the invention can select C as the raw material2～C24Preferably C2～C18Fatty alcohols, and ammonia, monomethylamine or dimethylamine. The molar ratio of the alcohol to the ammonia or amine may be 1: 1 to 12, preferably 1: 3 to 10. Generally, the amount of the same ammonia (amine) is increased with the carbon number of the alcohol in order to achieve a higher conversion, but the reactivity of ammonia, monomethylamine and dimethylamine is different for the same alcoholAs is well known to those of ordinary skill in the art. In order to reduce the using amount of ammonia (amine),lower ammonia (amine) alcohol ratios are used, although higher ammonia (amine) alcohol ratios are also possible.
The reaction temperature adopted by the method is controlled within the range of the activity temperature of the hydrogenation dehydrogenation catalyst, generally 150-300 ℃, preferably 170-250 ℃, and the system pressure determined by hydrogen is required to ensure that the alcohol raw material and the non-target aliphatic amine product are in liquid state, generally 0.1-5.0 MPa, preferably 0.1-3.5 MPa. Obviously, the pressure required for different alcohols will be different, with higher alcohols requiring lower pressures. The hydrogen amount in the reaction is controlled in the range of the molar ratio of alcohol to hydrogen of 1: 1-20, preferably 1: 3-15. The hourly space velocity (calculated by alcohol) of the raw material liquid can be 0.1-5.0 h-1Preferably 0.3 to 2.0 hours-1。
The reactor can be a fixed bed reactor or a kettle reactor. In the case of a fixed bed reactor, the lower feeding mode is adopted.
The hydrogenation and dehydrogenation catalyst is a conventional catalyst commonly used in the prior art and consists of a metal active component and a carrier. The metal active component comprises transition metal elements and compounds thereof, wherein the metal elements are selected from one or more of IB, VIB, VIIB and VIIIB groups, preferably one or more of chromium, molybdenum, manganese, iron, cobalt, nickel, platinum, copper and the like, and the metal compounds are preferably sulfides and oxides. The carrier may be alumina, silica, activated carbon, diatomaceous earth, kaolin, zeolite, etc. or a mixture thereof. The total content of the metal active components is 0.1-60 wt%, preferably 0.5-50 wt%, based on the total weight of the catalyst. Generally, the content of the noble metal may be smaller, and the content of the general metal may be larger. The catalyst is prepared according to methods well known to those of ordinary skill in the art.
The method for selectively preparing the alkyl monosubstituted aliphatic amine provided by the invention obviously improves the selectivity (not less than 90%) of the monosubstituted aliphatic amine in a reaction system on the premise of ensuring higher conversion rate (not less than 95%) and lower ammonia (amine) alcohol ratio, and can obtain a high-concentration target product in one step. In addition, the method has the advantages of simple and easy process, mild conditions and wide application range, can be used for preparing the amine compound with wider carbon number range, and can adopt a fixed bed reactor or a kettle reactor.
FIG. 1 is a process flow diagram using a fixed bed reactor.
FIG. 2 is a flow chart of a process employing a tank reactor.
The invention is further illustrated by the following examples and figures. The product compositions in the examples were analysed by chromatography.
Example 1
As shown in figure 1, lauryl alcohol, dimethylamine and hydrogen are continuously fed into a fixed bed reactor 1 in a way of feeding, the ratio of the lauryl alcohol, the dimethylamine and the hydrogen is 1: 3: 8(mol), the space velocity is 0.5(ml lauryl alcohol/ml catalyst. h), the reaction temperature is 210 ℃, the reaction pressure is 0.1-0.2 MPa, and the catalyst takes gamma-alumina as a carrier and is impregnated with 6.0% of metallic nickel, 6.5% of copper and 1.5% of molybdenum. And cooling the distillate by a condenser 2, and then feeding the distillate into a gas-liquid separator 3 for separation to obtain a product. Wherein the content of the dimethyl dodecyl tertiary amine is up to 93.7 percent, the content of the heavy component methyl didodecyl tertiary amine is only 2.6 percent, the conversion rate is 98.2 percent, and the selectivity of the dimethyl dodecyl tertiary amine is 95.4 percent. After reacting for 30h, the retention solution in the reactor contains 44.5 percent of dimethyl dodecyl tertiary amine and 44.8 percent of methyl didodecyl tertiary amine. The total selectivity of the dimethyl dodecyl tertiary amine is more than 90 percent.
Comparative example 1
Dodecanol, dimethylamine, hydrogen were continuously fed into the fixed bed reactor in the above-mentioned manner without any measures to separate the gas phase stream, and the rest of the reaction conditions were the same as in example 1. The product composition was 58.6% dimethyl dodecyl tertiary amine, 31.0% methyl didodecyl tertiary amine, 95.7% conversion, 61.4% dimethyl dodecyl tertiary amine selectivity.
Example 2
As shown in figure 2, n-octanol, ammonia and hydrogen are continuously introduced into an autoclave 4, the ratio of the three is 1: 8: 5(mol), the space velocityis 1.0(ml of n-octanol/ml of catalyst. h), the reaction temperature is 230 ℃, the reaction pressure is 1.5MPa, and the catalyst takes a mixed forming product of alumina and RE-Y type zeolite as a carrier, and is impregnated with 0.9% of metallic nickel and 9.7% of copper. And cooling the distillate by a condenser 2, and then feeding the distillate into a gas-liquid separator 3 for separation to obtain a product. The product composition was 92.9% n-octylamine, 3.9% di-n-octylamine, no tri-n-octylamine, 97.5% conversion, 95.3% n-octylamine selectivity. After 24h of reaction, the residue consists of 6.4% of n-octylamine, 47.9% of di-n-octylamine and 43.0% of tri-n-octylamine. The total selectivity of n-octylamine is more than 90%.
Comparative example 2
N-octanol was added to the autoclave once, ammonia and hydrogen were continuously introduced, the reaction conditions were the same as in example 2, and the reaction was carried out for 10 hours, with the compositions of n-octylamine 56.6%, di-n-octylamine 30.8%, tri-n-octylamine 2.4%, conversion rate 94.1%, and n-octylamine selectivity 60.1%.
Example 3
As shown in FIG. 2, n-butanol, ammonia and hydrogen were continuously introduced into an autoclave 2 at a ratio of 1: 3: 4(mol), an airspeed of 0.5(ml n-butanol/ml catalyst. h), a reaction temperature of 190 ℃ and a reaction pressure of 3.5MPa, and the catalyst was impregnated with 45% nickel using diatomaceous earth as a carrier. And cooling the distillate by a condenser 2, and then feeding the distillate into a gas-liquid separator 3 for separation to obtain a product. The product composition was 93.0% n-butylamine and 5.0% dibutylamine, with no tri-n-butylamine, conversion 98.2% and n-butylamine selectivity 94.7%. After 30 hours of reaction, the composition of the retentate in the reactor was 5.5% of n-butylamine, 46.0% of di-n-butylamine and 47.5% of tri-n-butylamine. The total selectivity of the n-butylamine is more than 90 percent.
As can be seen from the above examples and comparative examples, the selectivity of the mono-substituted aliphatic amine is significantly improved due to the novel reaction format employed in the process of the present invention.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99125946 CN1111153C (en) | 1999-12-13 | 1999-12-13 | Selective fatty amine preparing method |
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|---|---|---|---|
| CN 99125946 CN1111153C (en) | 1999-12-13 | 1999-12-13 | Selective fatty amine preparing method |
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| CN1299808A CN1299808A (en) | 2001-06-20 |
| CN1111153C true CN1111153C (en) | 2003-06-11 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070460B (en) * | 2011-02-16 | 2013-01-16 | 张家港市大伟助剂有限公司 | Method for synthesizing n-octyl amine |
| CN102614893B (en) * | 2012-03-04 | 2014-01-01 | 浙江建业化工股份有限公司 | Method for synthesizing tri-n-butylamine and catalyst used |
| CN103664633B (en) * | 2013-12-27 | 2015-08-19 | 大连百傲化学股份有限公司 | A kind of synthetic method of n-octyl amine |
| CN105254508A (en) * | 2015-10-26 | 2016-01-20 | 安徽广信农化股份有限公司 | Refining method for n-butyl isocyanate intermediate |
| CN105384643A (en) * | 2015-10-26 | 2016-03-09 | 安徽广信农化股份有限公司 | Exhaust gas treatment process for n-butyl isocyanate intermediate |
| CN105254509A (en) * | 2015-10-26 | 2016-01-20 | 安徽广信农化股份有限公司 | Production method for n-butyl isocyanate intermediate |
| CN111939925B (en) * | 2020-07-22 | 2022-12-06 | 江苏万盛大伟化学有限公司 | Catalyst for preparing n-octylamine and application thereof |
| CN112300006A (en) * | 2020-11-25 | 2021-02-02 | 淄博正大聚氨酯有限公司 | Method for preparing 1, 4-cyclohexyl dimethylamine by using hydroamination method |
| CN112973585B (en) * | 2021-02-07 | 2021-12-24 | 浙江大学 | A method of maintaining the stability of a polyolefin reactor |
| CN113385109B (en) * | 2021-06-24 | 2023-04-28 | 江苏万盛大伟化学有限公司 | Device and method for coproducing pentamethyldiethylenetriamine and trimethylhydroxyethyl ethylenediamine |
-
1999
- 1999-12-13 CN CN 99125946 patent/CN1111153C/en not_active Expired - Lifetime
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| CN1299808A (en) | 2001-06-20 |
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