Embodiment
The invention provides the method that a kind of ethene single stage method prepares thanomin, the method comprises: under the oxidative ammonolysis condition, ethene, ammonia, hydrogen peroxide and the catalyzer that contains HTS are contacted in organic solvent, and wherein, described contact is carried out in the presence of tensio-active agent.
All can realize purpose of the present invention according to the aforesaid method of the present invention, in order further to improve the transformation efficiency of reactant ethylene and the selectivity of target product thanomin, for the present invention, under the preferable case, by weight, the amount of described tensio-active agent is the 5-50000ppm of organic solvent, is preferably 150-1000ppm, more preferably 150-500ppm.
Among the present invention, as long as can realize goal of the invention of the present invention so that contain tensio-active agent in ethene, ammonia, hydrogen peroxide and the system that the catalyzer that contains HTS contacts in organic solvent, the adding mode of concrete Surfactant is without particular requirement, for example can in advance tensio-active agent be joined in the solvent and then introduce with solvent, also tensio-active agent can be introduced at last (being about to add again after all reactant feed are mixed), also can after having added the partial reaction raw material, be introduced again.No matter above-mentioned which kind of introduce the mode of tensio-active agent, all can realize goal of the invention of the present invention, and effect is suitable, and for the easy of actual mechanical process, by in advance tensio-active agent being joined in the liquid (such as organic solvent), then be incorporated in the system of contact with liquid on one side.
According to the present invention, as long as so that ethene, ammonia, contain tensio-active agent in hydrogen peroxide and the system that the catalyzer that contains HTS contacts and can realize goal of the invention of the present invention in organic solvent, optional a wider range of the kind of described tensio-active agent, can also can be water miscible tensio-active agent for oil-soluble tensio-active agent, in order further to improve the selectivity of target product thanomin, under the preferable case, described tensio-active agent is selected from tween (Tween) tensio-active agent, Ni Nale (Ninol) tensio-active agent, sapn (Span) tensio-active agent, TX-10 (alkylphenol polyoxyethylene) tensio-active agent, in OP-10 (Triton X-100) tensio-active agent and AEO-9 (fatty alcohol-polyoxyethylene ether) tensio-active agent one or more; One or more in Tween-60 (Tween-60), tween-80 (Tween-80), Arlacel-60 (Span-60), the Arlacel-80 (Span-80) more preferably.
Among the present invention, the described catalyzer that contains HTS can and/or contain the preformed catalyst of HTS for HTS.Generally speaking, rhythmic reaction adopts HTS as catalyzer, and successive reaction adopts and contains the preformed catalyst of HTS as catalyzer.
The method according to this invention, HTS described in the present invention can be the HTS (such as TS-1) of MFI structure, the HTS of MEL structure (such as TS-2), the HTS of BEA structure (such as Ti-Beta), the HTS of MWW structure (such as Ti-MCM-22), the HTS of two dimension hexagonal structure is (such as Ti-MCM-41, Ti-SBA-15), the HTS of MOR structure (such as Ti-MOR), at least a in the HTS (such as Ti-ZSM-48) of the HTS of TUN structure (such as Ti-TUN) and other structures.
Under the preferable case, described HTS is one or more in the HTS of the HTS of HTS, MEL structure of MFI structure and BEA structure, the HTS of MFI structure more preferably, more preferably described HTS is the MFI structure, HTS crystal grain is hollow structure, the radical length of the cavity part of this hollow structure is the 5-300 nanometer, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under 1 hour the condition at least 70 milligrams/gram, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and the desorption isotherm.
In the present invention, described HTS can be commercially available, and also can prepare, and prepares the method for described HTS for conventionally known to one of skill in the art, does not repeat them here.
The present invention to the condition of described oxidative ammonolysis without particular requirement, can for routine with the reaction conditions of HTS as the oxidation system of catalyzer, because explode easily when hydrogen peroxide exists with gaseous form, so the preferred hydrogen peroxide of the present invention provides with aqueous hydrogen peroxide solution.
Without particular requirement, for the present invention, the concentration of the hydrogen peroxide in the preferred described aqueous hydrogen peroxide solution is the 20-80 % by weight, is preferably the 30-70 % by weight to the concentration of hydrogen peroxide in the described aqueous hydrogen peroxide solution in the present invention.For example can be the hydrogen peroxide of 30 commercially available % by weight, 50 % by weight or 70 % by weight.
The present invention, preferably provides with ammoniacal liquor or liquefied ammonia without particular requirement the presentation mode of described ammonia, more preferably provides with liquefied ammonia.
According to of the present invention preferred embodiment a kind of, the described catalyzer that contains HTS is HTS, described hydrogen peroxide provides with aqueous hydrogen peroxide solution, described ammonia provides with liquefied ammonia, the mol ratio that the condition of described oxidative ammonolysis generally comprises ethene, ammonia and hydrogen peroxide is 1: 0.1-20: 0.1-10 is preferably 1: 1-15: 1-8; The mass ratio of organic solvent, water, catalyzer and ethene is 0.1-100: 0.01-50: 0.001-1: 1, be preferably 0.1-10: 0.1-30: 0.01-0.8: and 1,1-6: 3-15: 0.01-0.5 more preferably: 1; The temperature of contact is 20-260 ℃, is preferably 30-95 ℃; Pressure is 0.1-9MPa, is preferably 1-5MPa.Under these conditions, can select as required the time of required contact, be generally 0.1-20h, be preferably 0.3-4h.The previous reaction condition generally is fit to the rhythmic reaction system, also can be used for successive reaction, such as the reaction in the slurry bed.
According to another embodiment of the invention, the described catalyzer that contains HTS is the preformed catalyst that contains HTS, described hydrogen peroxide provides with aqueous hydrogen peroxide solution, described ammonia provides with liquefied ammonia, it is 20-260 ℃ that the condition of described oxidative ammonolysis generally comprises temperature, is preferably 50-95 ℃; Pressure is 0.1-9MPa, is preferably 1.5-5.0MPa; Liquid hourly space velocity is 0.01-10h
-1, be preferably 0.1-3h
-1The mol ratio of ethene, ammonia and hydrogen peroxide is 1: 0.1-20: 0.1-10 is preferably 1: 1-15: 1-8; The mass ratio of organic solvent, water and ethene is 0.1-100: 0.01-50: 1, be preferably 0.1-10: 0.1-30: and 1,1-5: 3-15 more preferably: 1; The agent oil volume is preferably 0.5-5 than for 0.01-10.The previous reaction condition generally is fit to the successive reaction system, such as successive reaction systems such as fixed beds.Liquid hourly space velocity described in the present invention is the definition of the conventional liquid hourly space velocity of using in this area, it is a kind of representation of air speed, its meaning is the per hour volume for the treatment of solution phase reaction thing of unit reaction volume (for the reaction of adopting solid catalyst, then being per volume of catalyst).The agent oil volume is the cumulative volume of catalyzer and the ratio of the cumulative volume of all liquid phase materials than the definition for the conventional agent oil volume ratio that uses in this area among the present invention.
The present invention to the described preformed catalyst of HTS that contains without particular requirement, can be the various moulding titanium-silicon molecular sieve catalysts that can be applicable to the successive reaction system, under the preferable case, the described preformed catalyst that contains HTS comprises carrier and HTS, wherein, take total catalyst weight as benchmark, the content of carrier is the 10-90 % by weight, and the content of HTS is the 10-90 % by weight.
The present invention to the carrier in the described preformed catalyst that contains HTS without particular requirement, can be the carrier of various preformed catalysts commonly used, for example heat-resistant inorganic oxide and/or the silicate of porous can be, concrete in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium white, Thorotrast, beryllium oxide and the clay one or more can be.More preferably, described carrier is one or more in aluminum oxide, silicon oxide, magnesium oxide and the zirconium white.
Among the present invention, the described forming method that contains the preformed catalyst of HTS can adopt technology well known in the art to carry out, can be prepared according to the method for the preformed catalyst of routine, mainly comprise the steps such as making beating, granulation and roasting, the present invention to this all without particular requirement.
As everyone knows, with HTS/H
2O
2Catalytic oxidation system, the effect of solvent mainly are in order to make reaction solution be homogeneous phase.Under this basic premise, the sterically hindered of solvent self can not be too large, can guarantee like this to react to carry out efficiently.And in the chosen process of solvent, those skilled in the art generally can select according to mentioned above principle, but the scope of selecting can not be confined to above-mentioned requirements, specifically must select according to concrete oxidative ammonolysis system.The present inventor finds that in the oxidation of ethylene system, at the solvent system that satisfies on the basis of aforementioned requirement, ethene all can be converted into the target product thanomin, but the yield of its transformation efficiency and target product is still limited.And the present inventor further finds, reaction effect is better during as solvent with in ketone, alcohols, carboxylic-acid and the halogenated organic alkane one or more, more preferably one or more in the halogenated organic alkane of the carboxylic acid of the alcohol of the ketone of C3-C10, C1-C10, C1-C10 and C1-C10; One or more in the halogenated organic alkane of the pure and mild C1-C6 of the ketone of C3-C6, C2-C6 more preferably are particularly preferably in acetone, butanone, ethanol, propylene glycol, the trimethyl carbinol, acetic acid and the trichloromethane one or more.
As previously mentioned, method provided by the invention can adopt periodical operation, also can operate continuously etc., the present invention to this without particular requirement.Feed way also can be any suitable way well known by persons skilled in the art, as when andnon-continuous operation manner is carried out, solvent, catalyzer can be added reactor after, add continuously ethene, ammonia, hydrogen peroxide and react; When in closed tank reactor, carrying out rhythmic reaction, catalyzer, solvent, ethene, ammonia and hydrogen peroxide can be added hybrid reaction in the still simultaneously.Can adopt the reactor commonly used such as fixed-bed reactor, slurry bed reactor when continuous mode carries out, when carrying out in fixed-bed reactor, feed way can add solvent, ethene, ammonia and hydrogen peroxide behind the catalyzer of packing into continuously; When in slurry bed reactor, carrying out, can be with adding ethene, ammonia, hydrogen peroxide react continuously after the catalysts and solvents making beating; The present invention, does not give unnecessary details at this all without particular requirement one by one to this.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.In embodiment and the Comparative Examples, used reagent is commercially available chemically pure reagent.
Used HTS (TS-1) catalyzer is (TS-1) sieve sample of preparing by the method described in the document [Zeolites, 1992, Vol.12 943-950 page or leaf], and titanium oxide content is 2.5 % by weight.
Used hollow HTS HTS is that (Hunan is built long company and made for the Industrial products of the described HTS of CN1301599A among the embodiment, be the HTS of MFI structure through X-ray diffraction analysis, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is the 15-180 nanometer; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
Among the present invention, thanomin refers to Monoethanolamine MEA BASF, diethanolamine and trolamine three's mixture.
Among the present invention, adopt gas-chromatography to carry out each analysis that forms in the system, undertaken quantitatively all can carrying out with reference to prior art by proofreading and correct normalization method, calculate on this basis the evaluation indexes such as the yield of transformation efficiency, product of reactant and selectivity.
In Comparative Examples and embodiment:
Embodiment 1
Be that (hydrogen peroxide provided with the aqueous hydrogen peroxide solution of 30 % by weight in 1: 10: 4.5 with ethene, hydrogen peroxide, liquefied ammonia, solvent acetone (containing tensio-active agent Tween-60 350ppm and Arlacel-80 150ppm) and catalyzer (TS-1) according to the mol ratio of ethene, liquefied ammonia and hydrogen peroxide, following examples are roughly the same) send into and carry out successive reaction in the reactor, and the mass ratio of ethene and catalyzer is 15: 1, the mass ratio of ethene and solvent is 1: 2.0, is that 35 ℃, pressure are to react under the 2.5MPa in temperature.Reacted 1 hour: conversion of ethylene is 99.4%, and the thanomin selectivity is 97.3%.
Embodiment 2
Be to send at 1: 8: 3 to carry out successive reaction in the reactor with ethene, hydrogen peroxide, liquefied ammonia, solvent trichloromethane (containing tensio-active agent tween-80 110ppm and Arlacel-60 160ppm) and catalyzer (TS-1) according to the mol ratio of ethene, liquefied ammonia and hydrogen peroxide, and the mass ratio of ethene and catalyzer is 50: 1, the mass ratio of ethene and solvent 1: 5.5 is that 55 ℃, pressure are to react under the 1.0MPa in temperature.Reacted 0.5 hour: conversion of ethylene is 98.3%, and the thanomin selectivity is 95.2%.
Embodiment 3
Be the mixture (containing tensio-active agent tween-80 65ppm, TX-10135ppm and AEO-925ppm) of acetone and trichloromethane and catalyzer (TS-1) according to the mol ratio of ethene, liquefied ammonia and hydrogen peroxide with ethene, hydrogen peroxide, liquefied ammonia, solvent be to send at 1: 4: 1.2 to carry out successive reaction in the reactor, the mass ratio of ethene and catalyzer is 30: 1, the mass ratio of ethene and solvent acetone 1: 2.5, the mass ratio of ethene and solvent trichloromethane 1: 1.5 is that 40 ℃, pressure are to react under the 1.5MPa in temperature.Reacted 1 hour: conversion of ethylene is 98.4%, and the thanomin selectivity is 93.7%.
Embodiment 4
Be the mixture (containing Ni Nale tensio-active agent 120ppm and Arlacel-80 90ppm) of the trimethyl carbinol and acetic acid and catalyzer (TS-1) according to the mol ratio of ethene, liquefied ammonia and hydrogen peroxide with ethene, hydrogen peroxide, liquefied ammonia, solvent be to send at 1: 3.5: 1 to carry out successive reaction in the reactor, and the mass ratio of ethene and catalyzer is 4: 1, the mass ratio of ethene and solvent tertiary butanol 1: 2.5, the mass ratio of ethene and solvent acetic acid 1: 0.8 is that 68 ℃, pressure are to react under the 1.2MPa in temperature.Reacted 3.5 hours: conversion of ethylene is 98.6%, and the thanomin selectivity is 92.8%.
Embodiment 5
Identical with the method for embodiment 1, different is that TS-1 is replaced by HTS, and reacted 0.5 hour: conversion of ethylene is 99.5%, and the thanomin selectivity is 98.6%.
Embodiment 6
Identical with the method for embodiment 1, different is, TS-1 (is to press prior art Corma etc. by Ti-MCM-41, Chem.Commun., method preparation described in 1994, the 147-148, titanium oxide content is 3 % by weight) replace, reacted 6 hours: conversion of ethylene is 94.1%, and the thanomin selectivity is 90.7%.
Embodiment 7
Identical with the method for embodiment 1, different is, TS-1 (is by J.Chem.Soc. such as prior art Takashi Tatsumi by Ti-Beta, Chem.Commun.1997, method preparation described in the 677-678, titanium oxide content is 2.6 % by weight) replace, reacted 4 hours: conversion of ethylene is 95.3%, the thanomin selectivity is 92.3%.
Embodiment 8
Identical with the method for embodiment 1, different is, contains tensio-active agent Tween-60 2500ppm and Arlacel-80 2000ppm in the solvent acetone, and reacted 3.5 hours: conversion of ethylene is 90.2%, and the thanomin selectivity is 84.3%.
Embodiment 9
Identical with the method for embodiment 1, different is: solvent is acetonitrile (containing tensio-active agent Tween-60 350ppm and Arlacel-80 150ppm).Reacted 3.5 hours: conversion of ethylene is 88.6%, and the thanomin selectivity is 51.4%.
Comparative Examples 1
Identical with the method for embodiment 1, different is not contain tensio-active agent in the solvent, and reacted 3.5 hours: conversion of ethylene is 85.3%, and the thanomin selectivity is 5.3%.
Can find out from embodiment and Comparative Examples: method target product selectivity of the present invention is high, and environmental friendliness, this shows that method of the present invention is very suitable for the industrial production of serialization.