CN1067374C - Two-step process of synthesizing primary behenic amine with methyl behenate - Google Patents
Two-step process of synthesizing primary behenic amine with methyl behenate Download PDFInfo
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- CN1067374C CN1067374C CN96117532A CN96117532A CN1067374C CN 1067374 C CN1067374 C CN 1067374C CN 96117532 A CN96117532 A CN 96117532A CN 96117532 A CN96117532 A CN 96117532A CN 1067374 C CN1067374 C CN 1067374C
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Abstract
The present invention relates to a method for synthesizing primary behenic amine. Saturated or unsaturated C8-22 fatty acid methyl ester prepared from vegetable oil and leftovers thereof or behenic acid methyl ester prepared from C22 monomers, gas ammonia and catalysts are heated and stirred to be ammonified, and products are cooled and separated from the catalysts to obtain behenic nitrile. The behenic nitrile is hydrogenized by adding Raney nickel, ammonia and water, the mixture is heated and stirred for hydrogenation reaction, and then, catalysts are separated, or primary behenic amine is prepared through distillation by pressure reduction. The purity can reach 98%, the investment is reduced, and the application of vegetable oil and leftovers thereof is developed. Pollution is reduced, and multiple products can be obtained.
Description
The present invention relates to synthetic mountain Yu uncle of two steps of methyl behenate that the tankage of the method, particularly vegetables oil of synthetic behenic amine of methyl behenate two step and processing thereof make by method.
Behenic amine (Behenic Primary amines) has another name called saturated C
22Carbon alkane primary amine, molecular formula CH
3(CH
2)
20CH
2NH
2, molecular weight 325, colourity 3, cation type solid compounds, purity can reach 98%.Dissolve in common organic solvents.Maximum iodine number 5.0, tool nontoxicity and noninflammability.
Behenic amine and derivative purposes thereof are extremely extensive, and many special purposes are arranged.Behenic amine can be used the attached knot of anticorrosion and anti-extra large bath class on Yu Haiyang naval vessel; The special purpose that also is used for the widely different commentaries on classics anti-friction composition of nuclear power station secondary; The derivative of be used as emulsifying agent, flotation agent (potassium and Repone K), dispersion agent, intermediate, acid purification agent, inhibiter, rubber and plastics releasing agent, disperse flushing agent, metal working lubricant, spinning and textile auxiliary agent, emulsifying agent being used ethoxylated amine, fuel oil (comprising gasoline, diesel oil and rocket fuel) adds agent agent etc.Behenic amine and fittings thereof can be applicable to industrial surface activity agent and technical fields such as daily-use chemical industry, oil field chemical, make the main raw material of production makeup and hair conditioner, cats product, the all respects that are used for industry such as spinning and weaving and agricultural, medicine, health and people's lives, with behenic amine and fittings thereof is the tensio-active agent of raw material production, have active high, emulsifying property, wettability, froth stability are good, characteristics such as sterilizing ability is strong, be specially adapted to emulsified bitumen, its effect is very good.
Prior art, in (1996) 12250～1225 pages of " the senior ア シ Application of straight chain shape is synthetic " literary compositions of " Japanese The Chemicals " the 87th volume o.11, put down in writing by the method for making of dodecyl to the octacosyl amine salt, adopt tetrahydro-lithium aluminium reducing acid amides and nitrile, after producing vitriol or hydrochloride or iodate, use sodium-hydroxide treatment, remove low-carbon (LC) amine, use ether recrystallization higher amines (C again through underpressure distillation
12～24Carbon amine) method, its building-up process complexity, the reductive agent and the solvent that are adopted cost an arm and a leg, and only are useful for the laboratory, and do not have industrial value.Having put down in writing with the unsaturated fatty acids in German Patent EP490382 is raw material, makes catalyzer with aluminium vanadine, zinc oxide, manganese salt or cobalt salt, and ammonification obtain fatty acid nitrile is made catalyzer with nickel or cobalt then, and C is made in hydrogenation
8-18The method of carbocyclic aliphatic amine.It is raw material that russian patent SU679572 has put down in writing with lipid acid, and VI or D II family metal oxide and aluminium are catalyzer, makes the method for fat primary amine under High Temperature High Pressure.At present, Shang Weijian is raw material with the methyl behenate, through the method for ammonification and the synthetic behenic amine of hydrogenation.
Given this, the object of the present invention is to provide a kind of is raw material with the methyl behenate, through the method for ammonification and the synthetic behenic amine of hydrogenation, and further provides a kind of methyl behenate made from vegetables oil and tankage thereof two to go on foot the method for synthetic behenic amine.
The method of synthetic behenic amine of two step of methyl behenate of the present invention comprises following process steps.
(1) ammonification: methyl behenate 500～1000 weight parts are heated to 100～120 ℃ of fusings, gas ammonia 2～10 weight parts of purity 98% are heated to 200 ℃, make catalyzer 5～50 weight parts with purity greater than 95% commercially available technical grade Witco 1298 Soft Acid zinc, belt stirrer is sent in metering respectively, the ammonification still of condenser, under normal pressure, be heated to 280～330 ℃, stir with 300～400r.pm speed, carried out aminating reaction 10～16 hours, the qualified methyl esters and the methyl alcohol of unreacted of aqueous phase is reclaimed in the cooling back, the methyl esters that unreacted is qualified drops into the recirculation reaction, prepared thick mountain Yu nitrile is carried out underpressure distillation, its residual voltage is controlled in 2～5 mmhg scopes, separating catalyst then makes purity and is 94～96% mountain Yu nitrile.Its methyl behenate transformation efficiency reaches 90～98%, and selectivity reaches 90～98%.
(2) hydrogenation: with 2～10 parts in mountain Yu nitrile 200～500 weight parts of purity 94～96%, hydrogen 25～50 weight parts of purity 99.0%, the Raney's nickel Ni-101P that makes catalyzer or Ni-102P1-15 weight part, the gas ammonia of making inhibitor and water, the hydrogenation still is sent in metering respectively, under ammonia dividing potential drop 0.8～2.0MPa, hydrogen dividing potential drop 1.5～2.0MPa, stagnation pressure 4.0MPa, 80～200 ℃ of conditions of temperature, stir with 500～1000r.p.m speed, reacted 2～6 hours, make thick behenic amine, behind separating catalyst, make the behenic amine of purity 90～96%.Wherein contain a small amount of secondary amine, tertiary amine and impurity.
Above-mentioned technology of the present invention can have following process for refining step, the behenic amine of purity 90～96% is sent into the underpressure distillation still, be not less than in 200～300 ℃ of tower still temperature, 190～290 ℃ of tower top temperatures, vacuum tightness-the 0.098MPa condition under, C is removed in underpressure distillation
8-20Aliphatic amide and obtain higher amines adds then and makes the dimethyl formamide of solvent or tetrahydrofuran (THF) extracts and recrystallization, makes purity and is not less than 98% behenic amine.
Above-mentioned methyl behenate is the saturated and unsaturated C that makes with vegetables oil and tankage thereof
8-22Fatty acid methyl ester is the unsaturated C of monomer through decompression film rectifying separation again
22Fatty acid methyl ester, the methyl behenate that the full hydrogenation of warp makes; And with above-mentioned identical method, from C
8-22Produce the saturated of any carbochain and unsaturated fatty acids methyl esters in the carbon.
Above-mentioned vegetables oil and tankage thereof are rapeseed oil and tankage thereof.Above-mentioned tankage are alkali refining soap stock and hydrolysis oil foot.
The index contrast of behenic amine that the inventive method makes and Harshaw company product is as follows:
| Product of the present invention | The Harshaw product | |
| Colourity | Do not survey | 3 |
| Iodine number | 1 | 5.0 |
| Secondary amine content (%) | ＜2 | ＜2 |
| Tertiary amine content (%) | ＜1 | ＜1 |
| Foreign matter content (%) | ＜1 | ＜1 |
| Primary amine content (%) | 98 | 94 |
The present invention's methyl behenate is that two step of the raw material method of synthetic behenic amine has following remarkable advantage and positive effect.
One, the present invention is raw material with the methyl behenate, compare with the technology that with lipid acid is raw material, hang down 30 ℃ because of the boiling point of its methyl esters is corresponding than lipid acid, purify easily, polymerization, to decompose raw material few, the reaction conditions gentleness, corrodibility is little, ammonification, hydrogenation can be carried out in carbon steel equipment, so facility investment is low, are easy to industrialization; Lipid acid system primary amine must carry out in 316 stainless steel equipments, and raw material decomposes, the polymerization loss is big, so the gross investment height.In addition, be the technology of raw material with the methyl behenate, water and methyl alcohol that reaction generates are easily discharged, and when being the raw material production aliphatic amide with lipid acid, the water of generation is difficult for discharging, and easily produces by product, influences primary amine quality product etc.
Two, adopt the method for the synthetic behenic amine of two step of methyl behenate that vegetables oil and tankage (wherein mainly comprising rapeseed oil and tankage thereof) thereof produce, opened up new way, turn waste into wealth for the utilization of the tankage of China's vegetables oil processing.This synthetic technology route three-waste pollution is few, the by-product C such as foreshot of rectifying and distillation fraction
8-20Aliphatic amide, raffinate, residue are useful matter, the tool nontoxicity.
Three, when producing saturated and unsaturated higher aliphatic acid methyl esters, can while by-product C
8-20Methyl esters both can be produced saturated C
22Behenic amine can be produced C again
8-20The lipid acid primary amine, promptly a set of equipment can be produced multiple aliphatic amide product.C
8-20The carbocyclic aliphatic methyl esters also can be produced Fatty Alcohol(C12-C14 and C12-C18) or replace diesel oil to use when not producing aliphatic amide.
Below, the invention will be further described to use embodiment again.
Embodiment 1
The present invention's methyl behenate is the method for synthetic behenic amine of two step of raw material, at first, and with vegetables oil, mainly select rapeseed oil and tankage thereof for use,, adopt common technology and equipment as alkali refining soap and hydrolysis oil foot, make methyl behenate, also available saturated and unsaturated C
8-22Fatty acid methyl ester is the unsaturated C of monomer component through decompression film rectifying separation
22Fatty acid methyl ester is made raw material through the methyl behenate that full hydrogenation is made, by following processing sequence operation operation.
1, ammonification
Methyl behenate 1000 grams with purity 90%～98%, be heated to 100～120 ℃, send into after waiting to melt and have agitator, in the ammonification still of 2 liters of thermometer and condenser, add purity then and make catalyzer greater than 95% zn cpds 10 grams, behind nitrogen replacement, feeding is through being preheated to about 200 ℃, gas ammonia 2～10 grams of purity 98%, stir and be warming up to about 280～330 ℃ with 300～400r.p.m speed, reacted 16 hours down in normal pressure, after reaction finishes cooling, reclaim the qualified methyl esters and the by-product methyl alcohol of unreacted of water, the methyl esters that unreacted is good returns the recirculation reaction.The crude product that stays at the bottom of the still carries out underpressure distillation, and residual voltage is controlled in 2～5 mmhg, separating catalyst then, and distillation makes mountain Yu nitrile, and its purity reaches 94～96%.Its methyl behenate transformation efficiency reaches 90～98%, and selectivity reaches 90～98%, and mountain Yu nitrile distillation yield reaches 97%.
2, hydrogenation
Mountain Yu nitrile 500 grams of the purity 94～96% that ammonification is made add in the hydrogenation stills, in the presence of Raney's nickel Ni-102P, feeding purity is 99.0% hydrogen, makes the water and gas ammonia 2～10 grams of inhibitor, in the ammonia dividing potential drop is 0.8～2.0MPa, and the hydrogen dividing potential drop is 1.5～2.0MPa.Stagnation pressure is about 4.0MPa, and temperature is under 80～200 ℃ of conditions, stirs with 500～1000r.p.m speed, reacts 2～6 hours, after the end, makes crude product, through the precipitate and separate catalyzer, makes behenic amine, and its purity reaches 90～96%.Mountain Yu nitrile transformation efficiency reaches 98～100%, and reaction yield reaches 98～97%, generally need not rectifying, as to the purity requirement height, also needs further refining.
3, refining
The behenic amine of the purity 90～96% that hydrogenation is made is sent in the underpressure distillation still, and its vacuum tightness is-0.098MPa, and tower still temperature is 200～300 ℃, and tower top temperature is 190～290 ℃, carries out underpressure distillation, removes C
18Following low-carbon (LC) amine, the dimethyl formamide of solvent is made in senior behenic amine employing or tetrahydrofuran (THF) extracts and recrystallization, reaches more than 98% by purified behenic amine purity
Implement 2
The present invention makes the method for synthetic behenic amine of raw material two step with methyl behenate, and its processing step, processing condition, equipment used are substantially the same manner as Example 1, and its characteristics are as follows.
1, ammonification.Raw material is selected methyl behenate 1000 grams of purity 98% for use; Catalyzer is selected manganese salt 10 grams for use; Reacted 12 hours; Make the mountain Yu nitrile of purity 96.7%.Its methyl behenate transformation efficiency 96.1%, reaction yield 96.0%, selectivity 93.0%, distillation yield 80%.
2, hydrogenation.Catalyzer is selected Raney's nickel Ni-101P for use
The behenic amine of making, purity 95.0%.Its mountain Yu nitrile transformation efficiency 100.0%; Reaction yield 96.0%, selectivity 94.8%.
Embodiment 3
The present invention makes the method for synthetic behenic amine of raw material two step with methyl behenate, and its processing step, processing condition, equipment used are substantially the same manner as Example 1, and its characteristics are as follows.
Ammonification.Raw material is selected methyl behenate 1000 grams of purity 84% for use; Catalyzer is selected Zinc compounds 10 grams for use, reacts 16 hours.Make the mountain Yu nitrile of purity 87.0%.Its methyl behenate transformation efficiency 89.8%, reaction yield 89.1%, selectivity 90.1%, distillation yield 97.0%.
The behenic amine purity of making is 79.7%.Its reaction yield 79.5%, selectivity 80.0%.
Embodiment 4
The present invention makes the method for the synthetic behenic amine of raw material two step method with methyl behenate, and its processing step, processing condition, use equipment are substantially the same manner as Example 1, and its characteristics are as follows.
Ammonification.Raw material is selected methyl behenate 400 grams of purity 84% for use; Catalyzer is selected Witco 1298 Soft Acid zinc 5～10 grams for use, and 320 ℃ of temperature of reaction were reacted 4 hours, made the mountain Yu nitrile of purity 89.1%.Its methyl behenate transformation efficiency 98.0%, reaction yield 88%, selectivity 89.0%, distillation yield 97.8%.
The behenic amine of making, purity 80.9%, its mountain Yu nitrile transformation efficiency 99.7%, reaction yield 80%, selectivity 79.1%.
Claims (4)
1. the method for synthetic mountain Yu acid of two steps of methyl behenate primary amine is characterized in that comprising following process steps,
(1) ammonification: methyl behenate 500～1000 weight parts are heated to 100～120 ℃ of fusings, gas ammonia 2～10 weight parts of purity 98% are heated to 200 ℃, the purity of making catalyzer is greater than 95% Witco 1298 Soft Acid zinc 5～50 weight parts, belt stirrer is sent in metering respectively, the ammonification still of condenser, under normal pressure, be heated to 280～330 ℃, stir with 300～400r.p.m speed, carried out aminating reaction 10～16 hours, the qualified methyl esters and the methyl alcohol of unreacted of aqueous phase is reclaimed in the cooling back, the methyl esters that unreacted is qualified drops into the recirculation reaction, prepared thick mountain Yu nitrile is carried out underpressure distillation, its residual voltage is controlled in 2～5 mmhg scopes, separating catalyst then makes the mountain Yu nitrile of purity 94～96%;
(2) hydrogenation: with mountain Yu nitrile 200～500 weight parts of purity 94～96%, hydrogen 25～50 weight parts of purity 99.0%, the Raney's nickel Ni-102P that makes catalyzer or Ni-101P1-15 weight part, make 2～10 parts of the water of inhibitor and gas ammonias, the hydrogenation still is sent in metering respectively, under ammonia dividing potential drop 0.8～2.0MPa, hydrogen dividing potential drop 1.5～2.0MPa, stagnation pressure 4.0MPa, 80～200 ℃ of conditions of temperature, stir with 500～1000r.p.m speed, reacted 2～6 hours, make thick behenic amine, behind separating catalyst, make the behenic amine of purity 90～96%.
2. the method for synthetic behenic amine of two step of methyl behenate as claimed in claim 1, it is characterized in that having following process for refining step, the behenic amine of purity 90～96% is sent into the underpressure distillation still, be not less than in 200～300 ℃ of tower still temperature, 190～290 ℃ of tower top temperatures, vacuum tightness-the 0.098MPa condition under, C is removed in underpressure distillation
8-20Aliphatic amide and obtain higher amines adds then and makes the dimethyl formamide of solvent or tetrahydrofuran (THF) extracts and recrystallization, makes purity and is not less than 98% behenic amine.
3. the method for synthetic behenic amine of two step of methyl behenate as claimed in claim 1 or 2 is characterized in that said methyl behenate is the saturated and unsaturated C that makes with rapeseed oil and tankage thereof
8-22Mixed methyl aliphatic ester, be the monomer component C through decompression film rectifying separation again
22, the methyl behenate that the full hydrogenation of warp makes.
4. the method for synthetic behenic amine of two step of methyl behenate as claimed in claim 3 is characterized in that said tankage are alkali refining soap stock and hydrolysis oil foot.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117532A CN1067374C (en) | 1996-04-23 | 1996-04-23 | Two-step process of synthesizing primary behenic amine with methyl behenate |
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|---|---|---|---|
| CN96117532A CN1067374C (en) | 1996-04-23 | 1996-04-23 | Two-step process of synthesizing primary behenic amine with methyl behenate |
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| Publication Number | Publication Date |
|---|---|
| CN1158843A CN1158843A (en) | 1997-09-10 |
| CN1067374C true CN1067374C (en) | 2001-06-20 |
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| CN96117532A Expired - Fee Related CN1067374C (en) | 1996-04-23 | 1996-04-23 | Two-step process of synthesizing primary behenic amine with methyl behenate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150820A2 (en) * | 1984-02-01 | 1985-08-07 | BASF Aktiengesellschaft | Process for the preparation of saturated primary amines |
| US5175370A (en) * | 1990-12-14 | 1992-12-29 | Hoechst Aktiengesellschaft | Process for the preparation of saturated primary fatty amines by hydrogenation of unsaturated fatty acid nitriles |
| JPH0632767A (en) * | 1992-07-15 | 1994-02-08 | Kao Corp | Production of amine |
-
1996
- 1996-04-23 CN CN96117532A patent/CN1067374C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150820A2 (en) * | 1984-02-01 | 1985-08-07 | BASF Aktiengesellschaft | Process for the preparation of saturated primary amines |
| US5175370A (en) * | 1990-12-14 | 1992-12-29 | Hoechst Aktiengesellschaft | Process for the preparation of saturated primary fatty amines by hydrogenation of unsaturated fatty acid nitriles |
| JPH0632767A (en) * | 1992-07-15 | 1994-02-08 | Kao Corp | Production of amine |
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| Publication number | Publication date |
|---|---|
| CN1158843A (en) | 1997-09-10 |
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