CN1398672A - Catalyst for liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine - Google Patents
Catalyst for liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine Download PDFInfo
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- CN1398672A CN1398672A CN 01126291 CN01126291A CN1398672A CN 1398672 A CN1398672 A CN 1398672A CN 01126291 CN01126291 CN 01126291 CN 01126291 A CN01126291 A CN 01126291A CN 1398672 A CN1398672 A CN 1398672A
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Abstract
The present invention relates to a catalyst for liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine and aims at solving the problems of long reaction period and low ethylamine yield. The solution is to use the catalyst with skeleton nickel as main catalyst, and W, RE element and at least one of Cr, P and B as cocatalyst. The catalyst is used in the industrial production of ethylamine.
Description
Technical field
The present invention relates to the catalyst that a kind of low concentration liquid-phase hydrogenatin prepares ethamine.
Background technology
Ethylamine compounds comprises ethamine (Ethanamine or Monoethylamine are called for short MEA), diethylamine (Diethylamine, vehicle economy A) and triethylamine (Triethylamine is called for short TEA).Ethylamine compounds is important organic intermediate, is widely used in fields such as agricultural chemicals, medicine, dyestuff, rubber, water treatment, adhesive and catalyst.Ethamine is colourless highly volatile liquid, poisonous, inflammable, be corrosive, main raw material and reagent as rubber chemicals, extractant, emulsifying agent, condensing agent, medicine, also be used for the production of dyestuff, surfactant, antioxidant, aircraft fuel and lubricant, most important purposes is synthetic triazine herbicide, wherein have " Atrazine " (Atrazine), " ametryn " (Ametryne), " bladex " (Cyanagine), " simajine " (Simazine).Diethylamine is colourless liquid, and is volatile, is corrosive.Main as producing herbicide (as benthiocarb etc.), N, N-diethyl ethylene diamine (DAPE), rubber accelerator is (as diethyl curing carbaminate, be called for short ZDC), ethyl ziram (Ethyl Ziram), tetraethylthiuram disulfide (being called for short TETD), alcohol inorganic agent ethyl thiuram (Ethylthiuram), beneficiation reagent, textile auxiliary, bactericide, corrosion inhibitor, polymerization inhibitor and antifreeze, medicine is (as procaine, chloroquine etc.), agricultural chemicals, all as intermediate, also can be used for synthetic ethylamino-ethanol in dyestuff and the organic synthesis as corrosion inhibiter and organic intermediate.Triethylamine is a colourless oil liquid, inflammable, main as organic solvent and organic synthesis intermediate, in synthetic resin is made as the catalyst of phosgenation polycarbonate and the polymerization inhibitor of tetrafluoroethene, also can be used for anti-hardening agent, the medicine in refining antibiotic, surfactant, the porcelain enamel industry, the chemical intermediate of ion exchange resin, triethylamine can be used as high-energy fuel.
The industrialized preparing process of ethamine class mainly contains: ethanol faces hydrogen ammoniation process, ethene ammoniation process, acetaldehyde ammoniation process.It is the main method of producing ethamine at present both at home and abroad that ethanol faces the synthetic ethamine of hydrogen ammoniation process.
It is reported, by C
2～C
6The synthetic C of hydrogenation of nitriles
2～C
6Organic amine be considered to a most economical process route, limited because of raw material sources, be difficult to form large-scale production, this method is produced the commercial Application of ethamine and is not appeared in the newspapers.Mainly from the by-product of producing acrylonitrile, along with expanding production of acrylonitrile, its output increases acetonitrile year by year, and the utilization of acetonitrile is also more and more important.Acetonitrile is made catalyst with noble metal or Fe, Co, Ni etc. under uniform temperature and pressure, gas phase or liquid phase (facing ammonia) hydrogenation makes ethylamine compounds.Can regulate proportion of products to satisfy market demand by changing material proportion and reaction condition.
A kind of manufacture method of ethamine class is disclosed among the clear 53-50109 of document Japan Patent JP.Being raw material with the crude acetonitrile that contains hydrogen cyanide in the document, in the presence of organic solvent, is catalyst with the skeleton nickel, in the hydrogen dividing potential drop is 0.5～10.0MPa, temperature is under 40～200 ℃ of conditions, carries out hydrogenation reaction and generates ethamine, and wherein organic solvent is ethanol or toluene.As calculated, the yield of its ethamine is up to 95.4%, and is also lower, in addition its reaction time longer, need reaction just can finish reaction in 3 hours, catalyst amount is bigger, is generally 12% of acetonitrile raw material weight, promptly its catalyst loading is lower.A kind of manufacture method of ethamine is disclosed among the clear 50-47909 of document Japan Patent JP.Being raw material with pure acetonitrile in the document, in the presence of organic solvent, is catalyst with the skeleton nickel that contains cobalt, is 4.0MPa in the hydrogen dividing potential drop, and temperature is to carry out hydrogenation reaction under 100 ℃ of conditions to generate ethamine, and wherein organic solvent is ethanol or toluene.Its reaction time is longer, needs 3 hours just can finish reaction, and the yield of ethamine is about 88% as calculated, and is also lower.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past document to exist the reaction time long in preparation ethamine process, and the defective that the yield of ethamine is lower provides a kind of catalyst of new low-concentration acetonitrile liquid phase system ethamine.This catalyst is used for the reaction of liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine, has the reaction time weak point, the characteristics that the ethamine yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine, comprise skeleton nickel, tungsten, thulium and be selected from co-catalyst at least a in chromium, boron or the phosphorus, wherein with atomic ratio measuring with respect to nickel, the consumption of tungsten is 0.001～1.0%, the consumption that is selected from co-catalyst at least a in chromium, boron or the phosphorus is 0～1.0%, and the consumption of thulium is 0.01～0.1%.
In the technique scheme, with the atomic ratio measuring with respect to nickel, the consumption preferable range of tungsten is 0.2～0.5%, and the consumption preferable range that is selected from co-catalyst at least a in chromium, boron or the phosphorus is 0.01～0.8%, and more preferably scope is 0.01～0.2%.The preferred version of thulium is for being selected from cerium, lanthanum, praseodymium or samarium, and more preferably scheme is for being selected from cerium or lanthanum, and with the atomic ratio measuring with respect to nickel, the consumption preferable range of thulium is 0.01～0.05%.
The used raw material of catalyst composition of the present invention is:
W elements: be selected from ammonium tungstate or other tungstates;
Chromium element: be selected from chromic anhydride, nitrate, chromate or bichromate;
Boron element: be selected from halogenation boron or hydroboron;
P elements: be selected from phosphate or phosphite;
Thulium: be selected from its oxide, nitrate or other soluble-salt.
Method for preparing catalyst of the present invention is as follows:
At first nickel-aluminium alloy is reacted with the sodium hydroxide solution of required reacting dose earlier, water cleans to neutral, add the tungsten of aequum then and be selected from that at least a and rare earth metal carries out modification among Cr, B or the P, through washing, ethanol washing 2～3 times and be kept in the ethanol.
Because nitrile catalytic hydrogenation system amine, reaction experience hydrogenation generates the pilot process of imines.The reactivity of imines is very high, easily take place further to react with reaction intermediate and principal product, by condensation, ammonia is separated, the crosslinked reaction generation secondary amine that waits, by-product such as tertiary amine and high-boiling components, influence reaction conversion ratio, selectivity and yield, therefore must improve the reactivity of catalyst, strengthen catalyst to the absorption of unsaturated intermediates such as imines or suppress its desorption, reduce the amount of free imines in the course of reaction as far as possible, improve hydrogenation reaction speed, shorten the reaction time, reduce the possibility that side reaction takes place, thereby reach the purpose of acetonitrile high conversion and primary amine high selectivity.From the hydrogenation of acetonitrile reaction mechanism mechanism of reaction, the interaction of intermediate product imines that desorption gets off on the catalyst and false add hydrogen product can aggravate the formation of high-boiling components.High-boiling components is adsorbed on catalyst surface can further reduce absorption to imines etc., forms vicious circle, causes the very fast inactivation of catalyst, therefore must strengthen the adsorption strength of catalyst active center.On the other hand, because the skeletal nickel catalyst activated centre is too much, the hydrogen supply amount is big, can cause the aggravation of product hydrogenolysis.The present invention is by introducing tungsten in skeleton nickel, strengthened the stability of catalyst, introduce at least a Cr of being selected from, B or P composition and thulium simultaneously, catalyst and its main reaction are adapted, strengthened the absorption of catalyst to unsaturated compounds such as imines, reduce the activity and the number of absorption hydrogen simultaneously, suppressed side reaction and deep hydrogenation, thereby improved catalyst to the active of main reaction and improved reaction conversion ratio and yield.Use catalyst of the present invention, be used for the reaction of low-concentration acetonitrile hydrogenation preparing ethamine, 60 ℃ of reaction temperatures, reaction pressure 2.5MPa, when being solvent with methyl alcohol-toluene, reacted 90～120 minutes, its acetonitrile conversion ratio reaches 100%, the ethamine yield can reach 98.5%, the highest by 95.4% than bibliographical information in the past increased closely 3.1%, and the reaction time was from original 3～4 hours, shorten to 1.5～2.0 hours, obtained effect preferably.
The present invention is further elaborated below by embodiment.
The specific embodiment [embodiment 1]
In 300 milliliters of reactors, the raw material acetonitrile is the crude acetonitrile of moisture 50% (weight), with the modified raney ni is catalyst, comprise tungsten and rare earth lanthanum in the catalyst, wherein with atomic ratio measuring with respect to Ni, Ni: W: La is 100: 1: 0.05, acetonitrile and hydrogen are 60 ℃ of reaction temperatures, reaction pressure is 2.5MPa, with methyl alcohol-toluene is solvent, wherein methyl alcohol: toluene (volume/volume)=1: 2.5, and solvent: acetonitrile (w/w) is 4: 1, catalyst/acetonitrile is 4.0% (weight), other adds 0.2 gram NaOH is reaction promoter, and low whipping speed is under 500 rev/mins, reacts 120 minutes, the acetonitrile conversion ratio is 100%, and the ethamine yield is 97.9% (weight).[embodiment 2～5]
Each operating condition and step according to embodiment 1, just change the composition of catalyst and the content of low-concentration acetonitrile raw material, wherein the raw material acetonitrile weight concentration among the embodiment 2,3,4,5 is respectively 30%, 40%, 70% and 80%, and its reaction result is listed in table 1.[comparative example 1]
According to each operating condition and the step of embodiment 1, just change the composition of catalyst, its reaction result is listed in table 1.
Table 1
| Sequence number | Skeletal nickel catalyst is formed (atomic ratio measuring) | Reaction temperature ℃ | Reaction pressure MPa | Acetonitrile conversion ratio % | Ethamine yield % (weight) |
| Embodiment 1 | ?Ni 100W 1.0La 0.05 | ????60 | ????2.5 | ??100 | ??97.9 |
| Embodiment 2 | ?Ni 100W 0.5Ce 0.02B 0.8 | ????60 | ????2.5 | ??100 | ??97.7 |
| Embodiment 3 | ?Ni 100W 0.001Pr 0.05 | ????60 | ????2.5 | ??100 | ??97.1 |
| Embodiment 4 | ?Ni 100W 0.2Cr 0.2La 0.05 | ????60 | ????2.5 | ??100 | ??98.5 |
| Embodiment 5 | ?Ni 100W 0.3Cr 0.01P 0.4La 0.01 | ????60 | ????2.5 | ??100 | ??98.0 |
| Comparative example 1 | ?Ni 100Co 2.1 | ????60 | ????2.5 | ??100 | ??87.6 |
Claims (7)
1, a kind of catalyst of liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine, comprise skeleton nickel, tungsten, thulium and be selected from co-catalyst at least a in chromium, boron or the phosphorus, wherein with atomic ratio measuring with respect to nickel, the consumption of tungsten is 0.001～1.0%, the consumption that is selected from co-catalyst at least a in chromium, boron or the phosphorus is 0～1.0%, and the consumption of thulium is 0.01～0.1%.
2,, it is characterized in that with atomic ratio measuring the consumption of tungsten is 0.2～0.5% with respect to nickel according to the catalyst of the described liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine of claim 1.
3,, it is characterized in that with atomic ratio measuring the consumption that is selected from co-catalyst at least a in chromium, boron or the phosphorus is 0.01～0.8% with respect to nickel according to the catalyst of the described liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine of claim 1.
4,, it is characterized in that with atomic ratio measuring the consumption that is selected from co-catalyst at least a in chromium, boron or the phosphorus is 0.01～0.2% with respect to nickel according to the catalyst of the described liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine of claim 3.
5,, it is characterized in that thulium is selected from cerium, lanthanum, praseodymium or samarium according to the catalyst of the described liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine of claim 1.
6,, it is characterized in that thulium is selected from cerium or lanthanum according to the catalyst of the described liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine of claim 5.
7,, it is characterized in that with atomic ratio measuring the consumption of thulium is 0.01～0.05% with respect to nickel according to the catalyst of the described liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011262915A CN1136978C (en) | 2001-07-20 | 2001-07-20 | Catalyst for liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011262915A CN1136978C (en) | 2001-07-20 | 2001-07-20 | Catalyst for liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine |
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| CN1398672A true CN1398672A (en) | 2003-02-26 |
| CN1136978C CN1136978C (en) | 2004-02-04 |
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| CNB011262915A Expired - Fee Related CN1136978C (en) | 2001-07-20 | 2001-07-20 | Catalyst for liquid phase hydrogenation of low-concentration acetonitrile to prepare ethylamine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302845C (en) * | 2004-03-11 | 2007-03-07 | 上海师范大学 | Co-Fe-B amorphous alloy catalyst, its preparation method and application |
| WO2008071090A1 (en) * | 2006-12-14 | 2008-06-19 | Bo Ma | A catalyst for hydrocracking high alcohols, its preparation method and application |
| CN108658787A (en) * | 2018-07-04 | 2018-10-16 | 浙江建业化工股份有限公司 | The preparation method of ethamine |
-
2001
- 2001-07-20 CN CNB011262915A patent/CN1136978C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302845C (en) * | 2004-03-11 | 2007-03-07 | 上海师范大学 | Co-Fe-B amorphous alloy catalyst, its preparation method and application |
| WO2008071090A1 (en) * | 2006-12-14 | 2008-06-19 | Bo Ma | A catalyst for hydrocracking high alcohols, its preparation method and application |
| CN108658787A (en) * | 2018-07-04 | 2018-10-16 | 浙江建业化工股份有限公司 | The preparation method of ethamine |
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| CN1136978C (en) | 2004-02-04 |
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Granted publication date: 20040204 Termination date: 20110720 |