CN101569862B - lower fatty amine catalyst - Google Patents
lower fatty amine catalyst Download PDFInfo
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- CN101569862B CN101569862B CN2008101053782A CN200810105378A CN101569862B CN 101569862 B CN101569862 B CN 101569862B CN 2008101053782 A CN2008101053782 A CN 2008101053782A CN 200810105378 A CN200810105378 A CN 200810105378A CN 101569862 B CN101569862 B CN 101569862B
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Abstract
The invention discloses a lower fatty amine catalyst belonging to a catalyst for ammonification and provides a catalyst which utilizes an alumina supporter to load cobalt functioning as an active component in order to solve the problem of low transformation ratio and selectivity existing in the prior art. The pore volume of a pore with the diameter of 70-170A in the alumina supporter is 35-55 percent of the total pore volume, and the pore volume of a pore with the diameter larger than 300A is smaller than 5 percent of the total pore volume. The catalyst has ideal catalytic activity and selectivity; and the proportion of generated primary amine, secondary amine and tertiary amine is easy to regulate.
Description
Technical field
The present invention relates to a kind of low-grade aliphatic amine synthetic catalyst, more particularly, the present invention relates to a kind of catalyst that in the presence of hydrogen, synthesizes C2～C4 fatty amine through ammonification.
Background technology
In chemical industry, aminated compounds comprises primary amine, secondary amine, tertiary amine, all is widely used in agricultural chemicals, dyestuff, medicine and other fields.They by alcohol and corresponding aldehyde, ketone, are facing in the presence of hydrogen state and the catalyst usually, carry out the preparation of hydrogen aminating reaction.The mechanism of hydrogen aminating reaction can be divided into for three steps: the first step, and the raw alcohol dehydrogenation generates aldehydes or ketones; In second step, aldehydes or ketones and ammonia addition generate imines; In the 3rd step, the further hydrogenation of imines generates amine.
U.S. Pat 2363721 provides a kind of compound of nickel and aluminium that uses to be catalyst, facing in the presence of hydrogen state and the catalyst, alcohol carries out the method that aminating reaction generates amine by the gas-solid bed bioreactor, but because contain primary in the end product, secondary, tertiary amine and reaction intermediate nitrile and unreacted alcohol, so the separation and purification of product is very difficult.
Chinese patent CN95117838.5 has reported a kind of aminating reaction catalyst, by carrier loaded Ni, Zn, Fe isoreactivity component, wherein active constituent shared percentage by weight in catalyst is 30-70Wt%, all the other are carrier, and the atomic ratio of active constituent is: Ni: Zn=1: 0.05～0.5, and Ni: Fe=1: 0.05～0.1.This catalyst can be applied to all kinds of aminating reactions, but reaction temperature is higher, still needs to improve its activity to reduce reaction temperature.Though generated primary, secondary, tertiary amine can regulate within the specific limits, adjustable range is less, and is especially relatively poor to the adjusting of tertiary amine.
Chinese patent CN02104202.0 provides a kind of lower fatty amine catalyst, by carrier loaded Co, Ca isoreactivity component, wherein active component accounts for the 10-50% of catalyst weight, the atomic ratio of active component is Co: Ca=1: 0.05-0.8, all the other are carrier, this catalyst can be used for the preparation technology of low-grade aliphatic amine, but Preparation of catalysts complex process, preparation condition and catalyst performance are difficult to grasp, ethanol conversion is on the low side simultaneously, selectivity is undesirable, generates more heavy ends and gas alkane light component.
Summary of the invention
Low and the side reaction problem of higher of conversion ratio that the inventor exists in order to overcome prior art has been carried out a large amount of deep researchs to activity of such catalysts component and carrier, discovers that the rerum natura of carrier is remarkable to the influence of catalyst performance.Through a large amount of tests, lower fatty amine catalyst of the present invention is proposed.Concrete technical scheme is as follows.
Lower fatty amine catalyst of the present invention contains active component cobalt and alumina support, and the bore dia in the described alumina support is that the pore volume in the hole of 70～170 dusts is 35%～55% of total pore volume, bore dia greater than the pore volume in the hole of 300 dusts less than 5% of total pore volume.
Preferably, the specific area of described alumina support is 100～180m
2/ g, the specific area of described catalyst is 70～130m
2/ g.
More preferably, the bore dia in the described alumina support is that the pore volume in the hole of 70～170 dusts is 40%～52% of total pore volume.
Further preferably, the bore dia in the described alumina support greater than the pore volume in the hole of 200 dusts less than 5% of total pore volume.
Preferably, with the catalyst benchmark and by weight percentage, described catalyst contains 15%～35% cobalt.
Lower fatty amine catalyst of the present invention can also contain other component, and alumina support also can comprise the component of improving performance, and for example lanthanum etc. is to improve catalyst stability.
The inventor carries out intensive research on the basis of existing technology, finds to use the preparing carriers lower fatty amine catalyst that the present invention limited, and catalyst activity of the present invention and selectivity all are higher than the catalyst among the CN02104202.0.Prepare in the process of ethamine in the ethanol ammonification, can generate a spot of heavy ends (industrial X of being referred to as by side reaction
3) and the gas light component (mainly comprise methane, ethane, ethene etc. by analysis, be referred to as C
1), in this process, use catalyst of the present invention and the X that generates
3And C
1Obviously be less than the amount of using among the CN02104202.0 that catalyst generated, produce this result's reason, infer and to cause by alumina support used in the present invention although can't get across in theory.
Catalyst of the present invention can prepare with conventional method, and the preparation method is not had special requirement, for example, takes by weighing a certain amount of carrier, and is dry then by infusion process load active component on carrier, roasting, and reduction obtains described catalyst prod at last.
Catalyst of the present invention is applicable to all kinds of aminating reactions, is particularly useful for the preparation of low-grade aliphatic amine.In the present invention, described low-grade aliphatic amine is meant the alkylamine that carbon number is less, refers in particular to C2～C4 fatty amine.
The method that catalyst of the present invention is used for synthetic fatty amine is as follows: adopt fixed bed reactors, above-mentioned catalyst is housed in the reactor, reaction condition is: normal pressure or pressurization, reaction temperature are 110～200 ℃, and the liquid volume hourly space velocity of alcohol (aldehydes or ketones) is 0.06～1h
-1, charge ratio is an alcohol: ammonia: hydrogen=1: 1～5: 1～5 (mol ratio), by above-mentioned condition alcohol (aldehydes or ketones), ammonia, hydrogen are fed fixed bed reactors, carry out aminating reaction, produce aminated compounds.
Compared with prior art, the present invention has the following advantages:
1, activity of such catalysts height of the present invention, the reaction condition gentleness of preparation fatty amine is carried out aminating reaction under normal pressure and lower temperature.
2, catalyst of the present invention has good amine selectivity, the heavy ends X of generation
3With gas light component C
1Few.
3, method for preparing catalyst of the present invention is simple, and catalyst has good stable.In fixed bed reactors, estimate 1000 hours continuously, catalyst performance stabilised.
4, catalyst range of application of the present invention is wider, can be used for producing low-grade aliphatic amines such as ethamine, propylamine and butylamine.
The specific embodiment
Embodiment 1
Present embodiment prepares catalyst A～F.
By the load constituent content, calculate and take by weighing cobalt nitrate wiring solution-forming soluble in water, adopted equivalent impregnation method oxide impregnation alumina supporter 0.5-2 hour, dried 2～6 hours down at 120 ℃, decompose down at 350～400 ℃ then.Can be by flooding several times and decomposing load cobalt component.Through the load of active component, obtain the aluminium oxide of load 15 weight %～35 weight % cobalts.The reactor of then catalyst being packed into feeds hydrogen down at 400～450 ℃, reduces 10 hours, obtains lower fatty amine catalyst of the present invention.Concrete data are listed in table 1.
Table 1 prepared catalyst data
Embodiment 2～7 and comparative example 1
Embodiment 2～7 is evaluate catalysts A～F respectively, and comparative example 1 is estimated the catalyst of embodiment 1 among the CN02104202.0.
The fixed bed pressurized reactor is adopted in the evaluation of catalyst.The consumption of each evaluate catalysts is 50ml, and product is analyzed with Agilent 6890 gas chromatographs.With ethanol is raw material, and reaction condition is: volume space velocity 0.72h during ethanol liquid
-1, ethanol: hydrogen: ammonia mol ratio 1: 3: 1.25,1.3MPa and 170 ℃, under this reaction condition, carry out aminating reaction and produce ethamine, reaction result is listed in the table 2.
Table 2 evaluating catalyst result
In table,
Conversion ratio=(reacted ethanol molal quantity)/(the ethanol molal quantity before the reaction) * 100
Certain components selection=(certain component molal quantity of generation)/(the ethanol molal quantity that reaction is consumed) * 100
Embodiment 8
Present embodiment is the feedstock production isopropylamine with the isopropyl alcohol, uses catalyst E.
In the same reactor of embodiment 2～7, the 50ml catalyst E that packs into, reaction condition is: volume space velocity 0.5h when pressure 1.1MPa, 175 ℃ of reaction temperatures, isopropyl alcohol liquid
-1, alcohol: hydrogen: ammonia=1: 3: 2.5, reaction result is listed in table 3.
Table 3 isopropylamine evaluating data
Embodiment 9
Present embodiment is the feedstock production n-butylamine with the n-butanol, uses catalyst B.
In the same reactor of embodiment 2～7, the 50ml catalyst B of packing into, reaction condition is: volume space velocity 0.5h when pressure 1.3MPa, 172 ℃ of reaction temperatures, n-butanol liquid
-1, alcohol: hydrogen: ammonia=1: 3: 2.5, reaction result is listed in table 4.
Table 4 n-butylamine evaluating data
Claims (4)
1. catalyst that is used to prepare low-grade aliphatic amine, described catalyst contains active component cobalt and alumina support, it is characterized in that, bore dia in the described alumina support is that the pore volume in the hole of 70～170 dusts is 35%～55% of total pore volume, bore dia greater than the pore volume in the hole of 300 dusts less than 5% of total pore volume, be benchmark and by weight percentage with the catalyst, described catalyst contains 15%～35% cobalt.
2. the catalyst that is used to prepare low-grade aliphatic amine as claimed in claim 1 is characterized in that, the specific area of described alumina support is 100～180m
2/ g, the specific area of described catalyst is 70～130m
2/ g.
3. the catalyst that is used to prepare low-grade aliphatic amine as claimed in claim 1 is characterized in that, the bore dia in the described alumina support is that the pore volume in the hole of 70～170 dusts is 40%～52% of total pore volume.
4. the catalyst that is used to prepare low-grade aliphatic amine as claimed in claim 1 is characterized in that, the bore dia in the described alumina support greater than the pore volume in the hole of 200 dusts less than 5% of total pore volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101053782A CN101569862B (en) | 2008-04-30 | 2008-04-30 | lower fatty amine catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101053782A CN101569862B (en) | 2008-04-30 | 2008-04-30 | lower fatty amine catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN101569862A CN101569862A (en) | 2009-11-04 |
| CN101569862B true CN101569862B (en) | 2011-11-30 |
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|---|---|---|---|
| CN2008101053782A Active CN101569862B (en) | 2008-04-30 | 2008-04-30 | lower fatty amine catalyst |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372638A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing monoisopropylamine |
| CN107915645A (en) * | 2017-10-12 | 2018-04-17 | 浙江晋巨化工有限公司 | A kind of n-butylamine production method |
| CN112169806A (en) * | 2020-10-21 | 2021-01-05 | 西安近代化学研究所 | Catalyst for synthesizing ethylamine and method for synthesizing ethylamine under normal pressure condition |
| US20230381757A1 (en) * | 2020-10-30 | 2023-11-30 | China Petroleum & Chemical Corporation | Amination catalyst and preparation and use thereof |
| US20230390747A1 (en) * | 2020-10-30 | 2023-12-07 | China Petroleum & Chemical Corporation | Amination catalyst and preparation and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436596A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process and application of catalyst for preparing lower C2-C4 alcohol |
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- 2008-04-30 CN CN2008101053782A patent/CN101569862B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1436596A (en) * | 2002-02-07 | 2003-08-20 | 中国石油化工股份有限公司 | Prepn process and application of catalyst for preparing lower C2-C4 alcohol |
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