CN101875014B - Catalyst for use in conversion of monoethanolamine and ammonia into ethylenediamine in hydrogen atmosphere - Google Patents
Catalyst for use in conversion of monoethanolamine and ammonia into ethylenediamine in hydrogen atmosphere Download PDFInfo
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- CN101875014B CN101875014B CN200910237770A CN200910237770A CN101875014B CN 101875014 B CN101875014 B CN 101875014B CN 200910237770 A CN200910237770 A CN 200910237770A CN 200910237770 A CN200910237770 A CN 200910237770A CN 101875014 B CN101875014 B CN 101875014B
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- monoethanolamine
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- ammonia
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Abstract
The invention discloses a catalyst for use in the conversion of monoethanolamine and ammonia into ethylenediamine in a hydrogen atmosphere. The active ingredient of the catalyst is transitional metal Ni or Co; an assistant is Re, Fe, Cu, Ru, B or other metal or one or several of oxides; a carrier may be Al2O3, SiO2, or the like. The catalyst may be prepared by one or several of the following methods: a precipitation method, an impregnation method and a hydrothermal synthesis method. When the catalyst of the invention is used in a fixed bed reactor, the monoethanolamine and liquid ammonia can be converted into various ammonia products, which are mainly the ethylenediamine, with high activity and high selectivity at a certain temperature and under hydrogen pressure and the action of the catalyst.
Description
Technical field
The present invention relates to a kind of under hydro condition monoethanolamine and ammonia be converted into the catalyst of ethylenediamine; At length relate to and a kind ofly be used under the hydro condition monoethanolamine and ammonia to be converted into ethylenediamine (EDA) be main, and the catalyst of coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and AEEA (AEEA) etc.
Background technology
The ethyleneamines series of products are to comprise ethylenediamine, diethylenetriamine, triethylene tetramine and polyethylene polyamine etc.; Wherein the most important thing is ethylenediamine; For the well sold and in short supply industrial chemicals in market, has purposes widely in fields such as epoxy curing agent, agricultural chemicals, high molecular polymers.Ethylenediamine mainly contains two kinds of preparation methods, and the one, dichloroethane law (EDC); The 2nd, monoethanolamine (MEA) method.Pluses and minuses are respectively arranged.The domestic EDC method that all adopts, the sodium chloride that this method by-product is a large amount of, equipment corrosion is serious, and energy consumption is big, domestic existing how tame manufacturer, but be in end-of-life state basically.The domestic never industrialized unit of MEA method.Therefore, the consumption of China's ethylenediamine mainly relies on import about 50,000 tons/year at present.
The sixties in last century, BASF AG realized the industrialization of MEA process; By monoethanolamine and ammonia under high pressure (greater than 20.0Mpa), reacting under the effect of hydrogen catalyst neutralisation; Major product is ethylenediamine (EDA); And coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and AEEA (AEEA) etc., adopt trickle bed reactor and catalyst such as Ni, Co and Cu.U.S.'s union carbide corporation then adopts Ni-Re-B/Al
2O
3Catalyst, reaction condition be gentle (15.0-18.0MPa and 140-160 ℃) relatively.
United States Patent (USP) 4,642,303 have reported that under the effect of Ni-Cu-Cr catalyst, the MEA aminating reaction helps the generation of EDA at low temperatures.United States Patent (USP) 3,068,290 have disclosed when Ni is catalyst based to be gone up the ammonia dividing potential drop and be 13-17Mpa, the selectivity of EDA is 70-90%, the ammonia dividing potential drop during less than 8.0Mpa the selectivity of EDA have only about 40%.United States Patent (USP) 5,068,330 have delivered and in Ni is catalyst based, have added Ir as auxiliary agent, have obtained good effect.United States Patent (USP) 4,992,587 adopt Ni and Co as active component, and porous metal oxide is a carrier, is auxiliary agent with Ru, and the conversion per pass of the catalyst MEA that makes through continuous impregnating, drying is more than 50%, and EDA compounds selectivity is about 70%.United States Patent (USP) 5,750,790 adopt transitional face Al
2O
3Load Ni and Re catalyst, the selectivity of MEA reactive activity and EDA all is improved, about 60%.United States Patent (USP) 6,534,441 have found at Ni-Re/Al
2O
3In added active component B after, the selectivity of EDA is brought up to more than 70%.
Summary of the invention
The object of the present invention is to provide a kind of catalyst that under hydro condition monoethanolamine and ammonia can be converted into ethylenediamine that is used for.
For realizing above-mentioned purpose, catalyst provided by the invention is made up of main active component, auxiliary agent and carrier three parts, and the weight of main active component is 1.0~50.0% of catalyst weight, and the weight of auxiliary agent is 0.1~20.0% of catalyst weight;
Main active component is metal Ni or Co;
Auxiliary agent is the metal of Re, Fe, Cu, Ru and B or in the metal oxide one or more;
Carrier is Al
2O
3Or SiO
2
Al in the carrier
2O
3Specific area be 100~400m
2/ g, average pore size is 5~100nm; Al preferably
2O
3Specific area be 150~350m
2/ g, average pore size is 8~80nm;
SiO in the carrier
2Specific area be 120~500m
2/ g, average pore size is 5~90nm; Carrier S iO preferably
2Specific area be 150~350m
2/ g, average pore size is 8~65nm.
Preparation of catalysts method of the present invention can adopt one or more combination in the precipitation method, infusion process, the hydrothermal synthesis method with active constituent loading on carrier.
Catalyst of the present invention monoethanolamine and ammonia under hydro condition are converted into the application in the reacting ethylenediamine, and its condition is: reaction temperature 135-155 ℃, hydrogen reaction pressure is 6.5-8.0MPa, and monoethanolamine liquid volume air speed is 0.35~0.65h
-1
Catalyst of the present invention carries out reduction activation earlier in hydrogen atmosphere before application: pressure is normal pressure~1.0MPa, and temperature is 100~500 ℃, and hydrogen gas space velocity is 500~5000h
-1
Compared with prior art, catalyst of the present invention can significantly reduce reaction pressure and energy consumption, improves the selectivity that under hydro condition monoethanolamine and ammonia can be converted into ethylenediamine.
The specific embodiment
Below set forth in detail content of the present invention.
Catalyst of the present invention is to be used for the reaction that under hydro condition monoethanolamine and ammonia can be converted into ethylenediamine.Catalyst is made up of main active component, auxiliary agent and carrier three parts.Main active component is that metal Ni and Co neutralize one or more, preferred Ni.Auxiliary agent is one or more in metals such as Fe, Re, B, Cu and Ru or the oxide.Carrier is selected Al for use
2O
3And SiO
2Deng.Monoethanolamine and ammonia are under hydro condition and this catalyst action in fixed bed reactors; But high activity, highly selective be converted into ethylenediamine be main various kinds of amine series products (particularly; It is main being converted into ethylenediamine (EDA), and coproduction diethylenetriamine (DETA), piperazine (PIP), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and AEEA (AEEA) etc.).Because this reaction condition and operating procedure etc. are not the emphasis that the present invention discusses, therefore no longer launch narration.
In the reaction system of the present invention, can be directly the monoethanolamine of liquid state and ammonia mixture be pumped in the preheater and H
2Enter into fixed bed reactors after being preheated to 150 ℃ after the mixing.In this process, need not to add any solvent dissolves or dilutes.
Reaction of the present invention can be adopted fixed bed reactors, also can adopt paste state bed reactor.Preferred immobilization bed bioreactor wherein.
Catalyst of the present invention, the preferable weight percentage of metal is 1.0~50.0%, optimum weight content is 5.0~25.0%; The preferable weight percentage of auxiliary agent is 0.1~20.0%, and best content is 0.5~10.0%; Carrier can select for use the specific area of aluminium oxide to be preferably 100~400m
2/ g, average pore size is 5~100nm, best specific area is 110~300m
2/ g, average pore size is preferably 5~100nm, and the optimum aperture is 10~80nm; Carrier also can adopt silica, and the preferable specific area of silica is 120~500m
2/ g, best specific area is 150~350m
2/ g, average pore size is preferably 5~90nm, and the optimum aperture is 8~65nm.
Reaction temperature of the present invention is 155 ℃, and hydrogen reaction pressure is 8.0MPa, and monoethanolamine liquid volume air speed is 0.5h
-1And NH
3: MEA: H
2=10: carry out evaluating catalyst under the condition of 1: 0.015 (mol ratio).The catalyst loading amount is 10ml.
Catalyst of the present invention can carry out activation through the hydrogen treat under the certain condition before using.Use the preferable condition of hydrogen activating catalyst to be: GHSV=2400h
-1, normal pressure, 375 ℃, 5 hours recovery times.
Through specific embodiment the present invention is further specified below.
Embodiment 1
Catalyst is 10%Ni-3.6%Re-1.2%B/Al
2O
3Take by weighing 10 gram Al
2O
3(20-40 order), through 500 ℃ of roastings 6 hours, configuration 12ml contained 3.654 gram Ni (NO before using
3)
2, 0.609 gram NH
4ReO
4With 0.806 gram H
3BO
3The aqueous solution, half of this aqueous solution of usefulness flooded above-mentioned Al
2O
3Carrier dries naturally, 120 ℃ of oven for drying 4 hours, 500 ℃ of roastings 5 hours.The above-mentioned Al that is loaded with Ni, Re and B metal of second half above-mentioned aqueous solution dipping
2O
3Carrier dries then naturally, 120 ℃ of oven for drying 4 hours, 500 ℃ of roastings 5 hours.Before using in 375 ℃ of hydrogen (normal pressure, 2400h
-1) reduction activation 5 hours.
Embodiment 2
Catalyst is 15%Ni-3.6%Re-1.2%B/Al
2O
3Except configuration 12ml contains 5.822 gram Ni (NO
3)
2, 0.647 gram NH
4ReO
4With 0.856 gram H
3BO
3Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 3
Catalyst is 20%Ni-3.6%Re-1.2%B/Al
2O
3Except configuration 12ml contains 8.279 gram Ni (NO
3)
2, 0.690 gram NH
4ReO
4With 0.913 gram H
3BO
3Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 4
Catalyst is 15%Ni-1.6%Re-1.2%B/Al
2O
3Except configuration 12ml contains 5.680 gram Ni (NO
3)
2, 0.336 gram NH
4ReO
4With 0.834 gram H
3BO
3Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 5
Catalyst is 15%Ni-3.0%Re/Al
2O
3Except configuration 12ml contains 5.694 gram Ni (NO
3)
2With 0.527 gram NH
4ReO
4Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 6
Catalyst is 15%Ni-1.0%Re-1.0%Ru/Al
2O
3Except configuration 12ml contains 5.626 gram Ni (NO
3)
2, 0.174 gram NH
4ReO
4With 0.247 gram RuCl
3Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 7
Catalyst is 10%Co/Al
2O
3Except configuration 12ml contains 3.449 gram Co (NO
3)
2Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 8
Catalyst is 15%Co-1.5%Re-1.2%B/Al
2O
3Except configuration 12ml contains 6.789 gram Co (NO
3)
2, 0.3.15 restrains NH
4ReO
4With 0.834 gram H
3BO
3Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 9
Catalyst is 4%Co-0.5%Ru-4%Fe-2%Ni/Al
2O
3Except configuration 12ml contains 0.629 gram Ni (NO
3)
2, 0.100 gram RuCl
3, 1.690 gram Fe (NO
3)
3With 1.211 gram Co (NO
3)
2Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 10
Catalyst is 15%Ni-3.6%Re-1.2B/SiO
2, except adopting SiO
2(20-40 order) carrier substitute for Al
2O
3Outward, remaining preparation process is identical with embodiment 2.
The catalyst of method for preparing is selected fixed bed reactors for use, is 155 ℃ in reaction temperature, and Hydrogen Vapor Pressure is 8.0MPa, NH
3: MEA: H
2=10: 1: 0.015 (mol ratio), MEA liquid air speed is 0.5h
-1, the reaction time is 50h, sample analysis.The HP-15 capillary chromatographic column, fid detector.Dimethyl formamide (DMFA) carries out quantitative analysis for interior mark.Reaction result is summarised in the table 1.
Press the catalyst of embodiment 4, reaction condition and raw material are formed, and have carried out more than 500 hour stability test, face hydrogen ammonification activity and selectivity and remain unchanged basically.
Adopt the Al of 2-3mm
2O
3Bead is as carrier, and the activity of such catalysts component is identical with embodiment 4 with auxiliary agent content, has carried out the catalyst feather weight and has amplified preparation; And at liter level single tube fixed bed reactors (internal diameter is 25mm; Height is 3000mm, and material is 316L, and the catalyst loading amount is 1 liter; Fill magnet ring for two sections) carried out reaction condition and embodiment 4 identical scale-ups, the result shows: activity of such catalysts and selectivity are basic identical.
Table 1: monoethanolamine and ammonia are converted into the evaluating catalyst result of ethylenediamine under the hydro condition
Claims (2)
- One kind under hydro condition monoethanolamine and ammonia be converted into the catalyst of ethylenediamine, composition is 20%Ni-3.6%Re-1.2%B/Al 2O 3The preparation method is following:Take by weighing 10 gram 20-40 order Al 2O 3, through 500 ℃ of roastings 6 hours, configuration 12ml contained 8.279 gram Ni (NO before using 3) 2, 0.690 gram NH 4ReO 4With 0.913 gram H 3BO 3The aqueous solution, half of this aqueous solution of usefulness flooded above-mentioned Al 2O 3Carrier dries naturally, 120 ℃ of oven for drying 4 hours, and 500 ℃ of roastings 5 hours,The above-mentioned Al that is loaded with Ni, Re and B metal of second half above-mentioned aqueous solution dipping 2O 3Carrier dries then naturally, 120 ℃ of oven for drying 4 hours, 500 ℃ of roastings 5 hours, before using in 375 ℃ of hydrogen, normal pressure, 2400h -1Reduction activation 5 hours.
- 2. the said catalyst of claim 1 monoethanolamine and ammonia under hydro condition is converted into the application in the reacting ethylenediamine, and condition is: reaction temperature 135-155 ℃, hydrogen reaction pressure is 6.5-8.0MPa, and monoethanolamine liquid volume air speed is 0.35~0.65h -1
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CN102658162B (en) * | 2012-04-13 | 2013-10-30 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing ethylene amine and method for preparing ethylene amine |
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CN108067289A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition |
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