CN1025732C - From C2-C9Method for preparing fatty amine from fatty alcohol - Google Patents
From C2-C9Method for preparing fatty amine from fatty alcohol Download PDFInfo
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- CN1025732C CN1025732C CN 90102887 CN90102887A CN1025732C CN 1025732 C CN1025732 C CN 1025732C CN 90102887 CN90102887 CN 90102887 CN 90102887 A CN90102887 A CN 90102887A CN 1025732 C CN1025732 C CN 1025732C
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- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 6
- 150000001412 amines Chemical class 0.000 title abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000002825 nitriles Chemical class 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 150000008431 aliphatic amides Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 25
- 150000003141 primary amines Chemical class 0.000 abstract description 16
- 150000003335 secondary amines Chemical class 0.000 abstract description 13
- 239000012467 final product Substances 0.000 abstract description 5
- 150000003512 tertiary amines Chemical class 0.000 abstract description 4
- -1 2-ethyl Chemical group 0.000 description 21
- QNIVIMYXGGFTAK-UHFFFAOYSA-N octodrine Chemical compound CC(C)CCCC(C)N QNIVIMYXGGFTAK-UHFFFAOYSA-N 0.000 description 10
- 229960001465 octodrine Drugs 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
From C2～C9The method for preparing fatty amine from fatty alcohol is mainly characterized by that its reaction pressure is close to normal pressure, and the reaction is implemented in two stages. The catalyst used in the first stage reaction has the general formula: xaYbZcOdThe typical scheme is as follows: CuSi1.5O3(ii) a The catalyst used in the second stage reaction has the general formula: a. thevBwCxDyOzThe typical scheme is as follows: CoZnSi7.5O8.5. Its advantages are reaction pressure close to normal pressure and no special requirement for equipment; the final product does not contain unconverted alcohol and intermediate nitrile, and the product is convenient to separate and refine; the selectivity of the primary amine is relatively high, and the remainder is primarily secondary amine, with the product being essentially free of tertiary amine.
Description
The invention belongs to method, relate to the required Preparation of catalysts of reaction by Fatty Alcohol(C12-C14 and C12-C18) system aliphatic amide.
In the presence of hydrogen, by alcohol and the method for ammonia by catalyzed reaction system amine for a long time the someone propose, as patent US2,365,721 provide the compound of a kind of Ni of use or Al to be catalyzer, carry out the method for gas-phase reaction system amine by alcohol and ammonia, hydrogen, because contain primary in the finished product simultaneously, secondary, three kinds of amine of uncle, and reaction intermediate nitrile and unreacted alcohol, and the boiling point of the amine of general identical alkyl, nitrile, alcohol is very approaching, so that the refining difficulty of product separation, thereby this method is difficult in industrial application.
Patent US3,022,349 proposes to solve the problems referred to above with two sections placed in-line reactions.In first section reaction, use the Cu-Al catalyzer, use the Ni-Ai catalyzer in second section reaction.For four alcohol below the carbon, this method effect is obvious, does not contain unreacted alcohol and intermediate nitrile in the finished product substantially, but the alcohol of higher carbon number is not prove effective, though the content of alcohol is very low in the outlet product of second section reaction, still has unconverted nitrile.For example when being raw material, 5.8% the own nitrile of 2-ethyl will be arranged in the product with the 2-Ethylhexyl Alcohol.And another bigger shortcoming of this method is that second section reaction catalyst system therefor is not high to the selectivity of primary amine, final product is that the once through yield of the primary amine of benchmark is 8.1% by ethanol system ethamine with charging alcohol, by propyl carbinol system n-Butyl Amine 99 is 24.9%, and by 2-Ethylhexyl Alcohol system 2 ethyl hexylamine be 23., %, all the other are secondary amine.Obtain more primary amine as hope, just this method is difficult to satisfy.
Patent FR1,468,354 have proposed a kind of reaction conditions is 30MPa, 300 ℃ high-pressure process, uses Co-Cr-P to be catalyzer, can reach 95.4% by the yield of 2-Ethylhexyl Alcohol system 2 ethyl hexylamine primary amine, secondary amine only is 1%.But, need to use the pressure-resistant equipment of high price, and complicated operation owing to adopted high pressure.In addition, so be difficult to make alcohol under the high pressure, especially carbon number is the alcohol gasification more than 7, thereby can only produce with liquid phase method, and continuous production is difficulty comparatively.
By alcohol and ammonia, H-H reaction system amine, the selectivity of primary amine why be difficult for high major cause be after the pure ammonification hydrogenation of nitriles of gained to become primary amine be two step reactions, its intermediate imines can be hydrogenated into primary amine, also can generate secondary amine with the harsh primary amine reaction that becomes, therefore add diacetyl oxide, sodium hydroxide when having the people to propose to react in the report, the primary amine that makes generation immediately salify to avoid and imine reaction generates secondary amine.But the separation of resultant affixture, decomposition, purification are very complicated, so have only the value of prepared in laboratory.
The purpose of this invention is to provide a kind of by C
2～C
9Fatty Alcohol(C12-C14 and C12-C18) is by the method for heterogeneous catalytic reaction system aliphatic amide, be characterized in that reaction pressure is near normal pressure, do not contain not segregative unreacting alcohol and intermediate nitrile in the reaction product, and the yield of primary amine is higher relatively, all the other are mainly secondary amine, and the ratio of primary amine and secondary amine also can be regulated by reaction conditions in the product.
Essence of the present invention is to divide two sections to carry out entire reaction, and has proposed two kinds and be respectively applied for first section reaction and second section catalyst for reaction.
To describe details of the present invention in detail below.
Feedstock fat alcohol and gaseous ammonia, hydrogen with certain proportion by preheater make the alcohol gasification and with ammonia, hydrogen thorough mixing, the temperature of preheater should be approaching with the temperature of first section reactor, generally is controlled at 190～300 ℃.Enter then in first section fixed-bed reactor that catalyzer is housed and react.In first section reactor, temperature of reaction is controlled between 170～300 ℃, and preferably 220～280 ℃, reaction pressure is 0～0.8MPa, preferably 0～0.5MPa.The product of first section reaction mainly is a nitrile except that primary amine, secondary amine, a small amount of tertiary amine, also has water, excess of ammonia, the hydrogen of a small amount of unreacted alcohol and generation.This product cuts primary amine, nitrile and unreacted alcohol mixture fraction and mixes with ammonia, hydrogen through condensation, distillation, enters in second section fixed-bed reactor that catalyzer is housed to carry out second section reaction.In second section reactor, temperature of reaction is 150～250 ℃, and preferably 200～240 ℃, reaction pressure is 0～1.0MPa, is preferably 0.15～0.4MPa.
The active ingredient of first section reactor catalyst system therefor has general formula:
Wherein X=Cu, Co or Ni, preferably Cu or Co, Y=Cr, Mo or W, preferably Cr or Mo, Z=Al or Si.A, b, c are the atomicity of respective element, when a=1, and b=0 or 0.01～0.8, C=1～5, d is the required oxygen atomicity of valency that satisfies other element.
The active ingredient of second section reactor catalyst system therefor has general formula:
Wherein A=Co, Ni, Pt, Pd or Raney Ni, preferably Co, Ni or Raney Ni, B=Zn, Cd, Cu, Mg, Ca or Mn, preferably Mg, Zn or Mn, C=V or Cr, D=Al or Si.V, w, x, y are the atomicity of respective element, when v=1, and w=0.1～2, x=0 or 0.1～1.5, y=1～15, z is the required oxygen atomicity of valency that satisfies other element.
Two kinds of equal available support of catalyzer or without carrier.When using carrier, various silica gel, aluminum oxide, diatomite, activated carbon all are fit to, or the wherein mixture of material more than two kinds of choosing.When using carrier, the content of active ingredient can be 5～50%(wt).
Two kinds of Preparation of catalysts methods are identical, can prepare from more than one aqueous solution that contains the compound of required element.PH value of aqueous solution is preferably 5 ± 2, and preparation temperature is 20～100 ℃.In general, prepare with the mixing solutions that contains required various elements, the grammeatom that can guarantee various elements in the catalyzer is than being desired value.Remove that water can carry out calcination then with co-precipitation or leaching method in the solution in the presence of air or oxygen, the calcination temperature of catalyzer is from 200～800 ℃, and calcination time can be from 30 minutes to 24 hours.Each element all combined as oxide compound with oxygen and exists during the calcination rear catalyst was formed.
In reaction process, the control of temperature and pressure is all influential to the transformation efficiency of the yield of product, alcohol.Generally, in first section reaction, temperature improves can make nitrile content increase in the outlet; The temperature raising makes secondary amine content increase in the final product in second section reaction, and pressure boost then can improve the selectivity of primary amine.
The residence time of reactant on catalyzer selected suitably also of crucial importance, is can not try one's best to be transformed first section reaction according to alcohol, and general air speed is got 130hr
-1～450hr
-1, with 300hr
-1～430hr
-1For good; Second section then according to nitrile whether fully by hydrogenation, general air speed is got 80hr
-1～500hr
-1, with 200hr
-1～300hr
-1For good.
Be to obtain optimum, enter alcohol, the amine of reactor, the mole ratio of hydrogen should be got an optimum proportion.To first section reaction, feed ammonia: alcohol is at least 1, is preferably (2～5): 1, and hydrogen: alcohol is (1～6): 1.The ratio increase of ammonia can improve the selectivity of primary amine in the charging, otherwise, then make secondary amine increase in the outlet, even more tertiary amine occurs.The ratio increase of hydrogen also can make secondary amine increase in the outlet.
Second section reaction, be the generation of inhibition secondary amine, and guarantee that residual alcohol all transforms that still need feed ammonia, hydrogen, ammonia with the ratio that reacts the raw material of gained by first section are:
Hydrogen: raw material is (1～8): 1, be preferably (1～6): and 1,
Ammonia: raw material is (1～8): 1, be preferably (1～4): 1.
Final step is that second section product that reacts gained carried out condensation, separation and purification, owing to do not contained unconverted alcohol and intermediate nitrile in the final product, so the separation and purification of product just can meet the demands with general distillatory method.
Compare with existing method, the invention has the advantages that:
1) reaction pressure does not have particular requirement near normal pressure to equipment;
2) final product does not contain unconverted alcohol and intermediate nitrile, and the separation and purification of product is convenient;
3) selectivity of primary amine is higher relatively, and all the other mainly are secondary amine, does not contain tertiary amine in the product substantially.
The present invention is further described below by embodiment, and described yield, transformation efficiency and selectivity definition are as follows:
Certain amine yield (%)=(certain amine mole number in the product/charging alcohol mole number) * 100
Transformation efficiency (%)=1-(unreacting alcohol mole number/charging alcohol mole number) * 100
Selectivity (%)=(yield/transformation efficiency) * 100
Embodiment 1:
1) Preparation of catalysts:
Take by weighing cupric nitrate 287.1g, be dissolved in the 200ml water, pour 8～10 order silica gel 107.2g into after being heated to whole dissolvings, be evaporated to driedly, activate 1 and 2 hour respectively at 300 ℃ and 500 ℃ then, then at 350～400 ℃ down with hydrogen reducings 4 hours.Make and be used for first section catalyst for reaction A:
Take by weighing Xiao Suangu 78.0g, zinc nitrate 72.0g adds 200ml water, after the heating for dissolving, adds 8～10 order silica gel 120.0g, be evaporated to do after, 450 ℃ of activation 2 hours, then with hydrogen stream 500 ℃ of reduction 4 hours down.Make and be used for second section catalyst for reaction B:
2) experiment:
Take by weighing catalyst A 83.8g and place φ 48 * 810 reaction tubess, in the middle of this reaction tubes is φ 8 thermopair covers, the porcelain grain filling of reaction tubes two end spaces, reaction tubes is connected with φ 4 * 300 preheating tubes, preheating tube is heated to 280 ℃, reaction tube temperature is controlled to be 260 ℃, and reaction pressure is a normal pressure, feeds raw material with following speed:
2-Ethylhexyl Alcohol 36.0ml/hr
Hydrogen 300ml/min
Ammonia 200ml/min
Product divides water to get the 29.7g/hr oil-phase product after condensation is collected, and successive reaction is after 120 hours, and product is analyzed with temperature programmed gas chromatography, and product consists of:
Octodrine 8.4%(wt) isooctyl alcohol 2.1%(wt)
Two (2-ethylhexyl) amine 25.8%(wt) different caprylic nitrile 59.5%(wt)
Three (2-ethylhexyl) amine 0.5%(wt)
Above-mentioned product distills, and gets 110 ℃/15mmHg cut in the past, and it consists of:
Octodrine 34.3%(wt) isooctyl alcohol 15.4%(wt)
Two (2-ethylhexyl) amine 1.5%(wt) different caprylic nitrile 48.3%(wt)
Above-mentioned cut is the raw material of second section reaction.
Take by weighing catalyst B 122.5g and place above-mentioned identical reaction unit, after reaction tubes is heated to 200 ℃ with following speed charging:
Hydrogen 240ml/min
Amine 160ml/min
Raw material 33.0ml/min
Reaction pressure is a normal pressure, gets product 26.7g/hr, analyzes to such an extent that product consists of:
Octodrine 89.5%(wt) isooctyl alcohol 1.5%(wt)
Two (2-ethylhexyl) amine 7.8%(wt) different caprylic nitrile 0.3%(wt)
Three (2-ethylhexyl) amine 0%(wt)
3) result
Behind second-stage reaction, be that the yield of various amine of benchmark is as follows with charging alcohol:
Octodrine 53.0%
Two (2-ethylhexyl) amine 41.4%
Transformation efficiency is 94.6%, and the octodrine selectivity is 56.0%, and two (2-ethylhexyl) amine selectivity is 43.8%
Embodiment 2:
1) Preparation of catalysts:
With embodiment 1.
2) experiment:
Replacing isooctyl alcohol with ethanol is raw material, and all the other are with embodiment 1.
The section of winning reaction product consists of:
Ethamine 12.3%(wt) ethanol 2.0%(wt)
Two-ethamine 20.1%(wt) acetonitrile 59.5%(wt)
Three-ethamine 5.0%(wt)
Second section reaction product consists of:
Ethamine 90.7%(wt) ethanol 0%(wt)
Two-ethamine 8.2%(wt) acetonitrile 0%(wt)
Three-ethamine 1.4%(wt)
3) result
The yield that with ethanol is the various amine of benchmark is as follows:
Ethamine 64.3%
Two-ethamine 30.2%
Transformation efficiency is 100.0%, and the ethamine selectivity is that 64.3%, two-ethamine selectivity is 30.2%
Embodiment 3
1) Preparation of catalysts:
With embodiment 1.
2) experiment:
Replacing isooctyl alcohol with propyl carbinol is raw material, and all the other are with embodiment 1.
The section of winning reaction product consists of:
Butylamine 10.1%(wt) butanols 2.5%(wt)
Two-butylamine 27.8%(wt) butyronitrile 54.8%(wt)
Three-butylamine 2.3%(wt)
Second section reaction product consists of:
Butylamine 90.5%(wt) butanols 0%(wt)
Two-butylamine 8.7%(wt) butyronitrile 0%(wt)
Three-butylamine 1.2%(wt)
3) result:
The yield that with the butanols is the various amine of benchmark is as follows:
Butylamine 61.8%
Two-butylamine 33.0%
Transformation efficiency is 100.0%, and the butylamine selectivity is that 61.8%, two-butylamine selectivity is 33.0%
Embodiment 4:
1) Preparation of catalysts:
Catalyst A is:
Catalyst B is:
2) experiment:
With embodiment 1.
3) result:
Behind second-stage reaction, be that the yield of various amine of benchmark is as follows with charging alcohol:
Octodrine 41.0%
Two (2-ethylhexyl) amine 45.3%
Transformation efficiency is 89.1%.
Embodiment 5:
1) Preparation of catalysts:
Catalyst A is:
Catalyst B is:
2) experiment:
With embodiment 1.
3) result:
Behind second-stage reaction, be that the yield of various amine of benchmark is as follows with charging alcohol:
Octodrine 39.8%
Two (2-ethylhexyl) amine 55.2%
Transformation efficiency is 96.7%.
Embodiment 6:
1) Preparation of catalysts:
With embodiment 1.
2) experiment:
Change the feeding speed of hydrogen and ammonia, all the other are with embodiment 1.
First section reaction:
Hydrogen 300ml/min ammonia 120ml/min
Product consists of:
Octodrine 1.7%(wt) isooctyl alcohol 3.7%(wt)
Two (2-ethylhexyl) amine 39.1%(wt) different caprylic nitrile 44.2%(wt)
Three (2-ethylhexyl) amine 0.5%(wt)
Second section reaction:
Hydrogen 320ml/min
Ammonia 80ml/min
Product consists of:
Octodrine 71.8%(wt) isooctyl alcohol 2.2%(wt)
Two (2-ethylhexyl) amine 24.8%(wt) different caprylic nitrile 0.2%(wt)
Three (2-ethylhexyl) amine 0%(wt)
3) result
Behind second-stage reaction, be that the yield of various amine of benchmark is as follows with charging alcohol:
Octodrine 35.9%
Two (2-ethylhexyl) amine 55.5%
Transformation efficiency is 98.9%.
Claims (7)
1, a kind of by C
2～C
9The method of Fatty Alcohol(C12-C14 and C12-C18) system aliphatic amide, this method comprises:
The Fatty Alcohol(C12-C14 and C12-C18) heating and gasifying mixes with gaseous ammonia, hydrogen, and mixing back unstripped gas enters first section reactor and carries out catalyzed reaction, and temperature of reaction is 170～300 ℃, and reaction pressure is 0～0.8MPa, distills after its product condensation;
Cut primary amine, unreacting alcohol and mixture of nitriles cut enter second section reactor and feed gaseous ammonia, hydrogen is proceeded catalyzed reaction, temperature of reaction is 150～250 ℃, the pressure of reaction is 0～1.0MPa, the product condensation is refining then, it is characterized in that:
The general formula of the active ingredient of first section reactor catalyst system therefor is:
Wherein X=Cu, Co or Ni, Y=Cr, Mo or W, Z=Al or Si, a, b, c are the atomicity of respective element, when a=1, during b=0,0.01～0.8, C=1～5, d is the required oxygen atomicity of valency that satisfies other element,
This catalyzer available support or without carrier, used carrier is silica gel, aluminum oxide, diatomite or activated carbon when with carrier, or the mixture of material more than two kinds wherein, the weight percentage of active ingredient is 5～50%;
The general formula of the active ingredient of second section reactor catalyst system therefor is:
Wherein A=Co, Ni, Pt, Pd or RaneyNi, B=Zn, Cd, Cu, Mg, Ca or Mn, C=V or Cr, D=Al or Si, v, w, x, y are the atomicity of respective element, when v=1, and w=0.1～2, x=0 or 0.1～1.5, y=1～15, z is the required oxygen atomicity of valency that satisfies other element
This catalyzer available support or without carrier, used carrier is silica gel, aluminum oxide, diatomite or activated carbon when with carrier, or the mixture of material more than two kinds in the base, the weight percentage of active ingredient is 5～50%.
2, by the described method of claim 1, the air speed that it is characterized in that first section reactor internal reaction thing is 130hr
-1～450hr
-1, the air speed of second section reactor internal reaction thing is 80hr
-1～500hr
-1
3, by the described method of claim 1, it is characterized in that:
The mole ratio of first section reaction mass is:
Ammonia: alcohol is at least 1,
Hydrogen: alcohol is (1～6): 1;
Second section reaction feeding gaseous hydrogen, ammonia with the ratio that reacts the raw material of gained by first section are:
Hydrogen: raw material is (1～8): 1.
Ammonia: raw material is (1～8): 1.
4, by the described method of claim 3, it is characterized in that:
The ammonia of first section reaction mass mole ratio: alcohol is (2～5): 1;
Second section reaction feeding gaseous hydrogen, ammonia with the ratio that reacts the raw material of gained by first section are:
Hydrogen: raw material is (1～6): 1,
Ammonia: raw material is (1～4): 1.
5, by the described method of claim 1, it is characterized in that:
X=Cu or Co in first section reactor catalyst system therefor, Y=Cr or Mo, Z=Al or Si;
A=Co, Ni or RaneyNi in second section reactor catalyst system therefor, B=Mg, Zu or Mn, C=V or Cr, D=Al or Si.
6, by the described method of claim 1, the temperature of reaction that it is characterized in that first section reaction is 200～290 ℃; The temperature of reaction of second section reaction is 170～250 ℃.
7, by the described method of claim 1, the reaction pressure that it is characterized in that first section reaction is 0～0.5MPa; The reaction pressure of second section reaction is 0.15～0.4MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90102887 CN1025732C (en) | 1990-06-30 | 1990-06-30 | From C2-C9Method for preparing fatty amine from fatty alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90102887 CN1025732C (en) | 1990-06-30 | 1990-06-30 | From C2-C9Method for preparing fatty amine from fatty alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1057831A CN1057831A (en) | 1992-01-15 |
| CN1025732C true CN1025732C (en) | 1994-08-24 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90102887 Expired - Fee Related CN1025732C (en) | 1990-06-30 | 1990-06-30 | From C2-C9Method for preparing fatty amine from fatty alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1025732C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047960C (en) * | 1995-12-15 | 2000-01-05 | 化学工业部北京化工研究院 | Catalyst for ammoniation reaction |
| CN101844987B (en) * | 2010-05-25 | 2012-12-26 | 张家港市大伟助剂有限公司 | Preparation method of bi-(2-ethylhexyl) |
| CN111871429B (en) * | 2020-08-28 | 2022-07-12 | 万华化学集团股份有限公司 | Raney catalyst and preparation method thereof, and method for preparing gamma-ketene from alpha, gamma-dienone |
| CN113548883B (en) * | 2021-07-08 | 2022-11-04 | 太原理工大学 | A kind of continuous white light transparent ceramic material with stable output and preparation method and application thereof |
-
1990
- 1990-06-30 CN CN 90102887 patent/CN1025732C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1057831A (en) | 1992-01-15 |
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