CN108067289A - Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition - Google Patents

Abstract

A catalyst for converting monoethanolamine and ammonia into ethylenediamine and piperazine under the condition of hydrogen. The catalyst consists of three parts: main active component, auxiliary agent and carrier. The main active component includes transition metal Ni, Cu or Co; The auxiliary agent is one or several metals or oxides such as Fe, Cr, Re, Ru, B, Mg, etc.; the carrier is molecular sieve H-ZSM-5, H-β, H-MOR or H-Y, etc. The preparation method of the catalyst of the present invention is one or a combination of an impregnation method or a precipitation method. The catalyst of the present invention is in a fixed-bed reactor, under certain temperature, hydrogen pressure and a certain amount of catalyst conditions, monoethanolamine and liquid ammonia can be converted into target amine products ethylenediamine and ethylenediamine with high conversion rate and high selectivity. Piperazine.

Description

Catalyst and its preparation and application in the production of ethylenediamine and piperazine under the condition of hydrogen

technical field

The invention relates to a catalyst for converting monoethanolamine and ammonia into ethylenediamine and piperazine under the condition of hydrogen, and relates in detail to a catalyst for converting monoethanolamine and ammonia into ethylenediamine (EDA) and piperazine under the condition of hydrogen. Diethylenetriamine (DETA), aminoethylpiperazine (AEP), hydroxyethylpiperazine (HEP) and hydroxyethylethylenediamine (AEEA) are co-produced as catalysts.

Background technique

Ethyleneamine products include ethylenediamine, diethylenetriamine, triethylenetetramine, polyethylenepolyamine and cyclic amines such as piperazine. Among them, ethylenediamine and piperazine are chemical raw materials that are in short supply in the market and are widely used in many fields. As important chemical raw materials and fine chemical intermediates, ethylenediamine and piperazine can be used in industries such as polymer compounds, pharmaceuticals, dyes, and pesticides; they can also be used in the production of chelating agents, insect repellents, soil conditioners, lubricants, Rubber accelerators and other products; it can also be used in the production of epoxy resin curing agents, emulsifiers, antifreeze agents, organic solvents and chemical analysis reagents, etc., with a wide range of uses.

At present, the methods for synthesizing ethyleneamine in industry are mainly ethylene dichloride (EDC) method and ethanolamine (MEA) method. The EDC method has the disadvantages of severe equipment corrosion and high energy consumption, so this process is gradually being eliminated. The MEA method has the advantages of low investment in the process route and low environmental pollution. According to different process routes, it is divided into two types: reductive amination method and condensation amination method: the reductive amination method reacts under high-pressure hydrogenation conditions, and the product is chain amine. The ethylenediamine is mainly produced; the condensation amination method does not require hydrogen, and the required reaction temperature is high. The reaction products are mainly cyclic amines, such as piperazine and its derivatives.

In the 1960s, BASF realized the industrialization of the MEA method for the first time. The MEA method developed by BASF uses a trickle bed reactor, using metals such as Ni, Co, and Cu as catalysts, and reacting under high pressure (20.0-30.0MPa). The products include ethylenediamine, diethylenetriamine, and hydroxyethyl Ethylenediamine, piperazine, aminoethylpiperazine, hydroxyethylpiperazine, etc., among which ethylenediamine is the main product. In China, Shandong Union Chemical Industry Co., Ltd. adopted the MEA process developed by the Dalian Institute _of Chemical Physics, Chinese Academy of Sciences _, and realized the industrialization of China's MEA method for the first time to prepare _{ethyleneamine} . Metals such as Ni or Co are used as catalysts, the reaction temperature is 135-155°C, the pressure is 6.5-8.0MPa, and the product is mainly ethylenediamine.

The reductive amination method of monoethanolamine in the presence of a catalyst produces ethyleneamine. Since the product amines have higher reactivity compared with liquid ammonia, the reaction inevitably generates complex polyalkylenepolyamine by-products, making ethyleneamine The yield of diamine and piperazine is reduced, which increases the cost of separation. Commonly used methods can improve the selectivity of the product ethylenediamine, but the selectivity of the product piperazine is low, which affects the production capacity of piperazine. Monoethanolamine adopts the condensation amination method to produce ethyleneamine. Because the reaction mechanism is different from the reductive amination method, the conversion rate of monoethanolamine is high, but the products are mainly piperazine and its derivatives, and the selectivity of ethylenediamine is low. The temperature required for the reaction is high and the energy consumption is large. Therefore, there is a need for a catalyst that can not only improve the selectivity of target products ethylenediamine and piperazine, but also maintain a higher conversion rate of monoethanolamine.

US Patent No. 4123462 adopts different supports to load metal Ni, and after adding additive Re, not only the conversion rate of amination reaction is improved, but also the selectivity of the target product ethylenediamine is improved. In addition, the patent found that the type and specific surface area of the carrier have a certain influence on the activity of the catalyst. US Patent 4209424 used Al ₂ O ₃ as a carrier to prepare nickel-based metal catalysts. It was found that the catalyst activity was significantly improved after adding additives Na and Rh. US Patent No. 5,750,790 reported Ni-Re catalysts supported by different supports, and found that the use of transition phase Al ₂ O ₃ support is beneficial to improve the catalyst activity and the selectivity of ethylenediamine, while reducing the selectivity of rings. U.S. Patent 6534441 uses SiO ₂ -Al ₂ O ₃ supported Ni-Re-B catalyst for reductive amination to produce ethyleneamine, the additives Re and B improve the stability of the catalyst, and the selectivity of ethylenediamine is increased to 70 ~80%. International patent 2013152548 uses ammoniated SiO ₂ or Al ₂ O ₃ as the carrier, and the active metal is Ni or Co. After adding additives Re and B, the conversion rate of monoethanolamine and the selectivity of ethylenediamine are significantly improved. Chinese patent 101215239 uses condensation amination method to jointly prepare ethylenediamine and aminoethylpiperazine in two steps: in the first step, monoethanolamine and ammonia react to form ethylenediamine in the presence of condensation amination catalyst phosphorus-modified mordenite , piperazine and other amines, and the product is separated to obtain the product ethylenediamine; in the second step, piperazine and unreacted monoethanolamine continue to react in the presence of silicon-modified ZSM-5, and after separation and purification, the target product is obtained Aminoethylpiperazine.

There are one or more problems in the preparation of ethyleneamine by using the catalyst of the above prior art, such as low conversion rate of monoethanolamine, low selectivity and poor stability of ethylenediamine or piperazine.

Contents of the invention

The object of the present invention is to provide a kind of catalyst that can be converted into ethylenediamine and piperazine for monoethanolamine and ammonia under the condition of facing hydrogen, and described catalyst can realize one or more in the following: (1) increase monoethanolamine The conversion rate of ethanolamine and ammonia, (2) improve the selectivity of target amines ethylenediamine and piperazine, (3) make monoethanolamine hydrogenation amination prepare ethylenediamine and piperazine and realize under lower reaction pressure, ( 4) reducing the energy consumption of preparing ethylenediamine and piperazine by hydroamination of monoethanolamine, (5) improving the stability of the method, and (6) realizing easy operation.

In order to achieve the above object, the catalyst provided by the invention comprises main active components, auxiliary agents and carriers, the weight of main active components accounts for 1.0～60.0% of catalyst weight, preferably 10.0～25.0%, and the weight of auxiliary agents accounts for 1% of catalyst weight. 0.1-30.0%, preferably 1.0-10.0%:

The main active component is one or more than two transition metals Ni, Cu or Co, preferably metal Ni;

The auxiliary agent is one or more than two kinds of metals or oxides among Fe, Cr, Re, Ru, B, Mg, preferably the auxiliary agents Re, B, Mg;

The carrier is H-ZSM-5, H-β, H-MOR or H-Y molecular sieve;

The specific surface area of H-ZSM-5 in the carrier is 300-800m ² /g, and the silicon-aluminum ratio is 10.0-200.0; preferably, the specific surface area of H-ZSM-5 is 450-600m ² /g, and the silicon-aluminum ratio is 50.0-200.0. 100.0;

The specific surface area of H-β in the carrier is 200-800m ² /g, and the silicon-aluminum ratio is 20.0-80.0; preferably, the specific surface area of H-β is 400-700m ² /g, and the silicon-aluminum ratio is 40.0-65.0;

The specific surface area of H-MOR in the carrier is 200-700m ² /g, and the silicon-aluminum ratio is 5.0-30.0; preferably, the specific surface area of H-MOR is 350-500m ² /g, and the silicon-aluminum ratio is 10.0-20.0;

The specific surface area of HY in the carrier is 300-1000m ² /g, and the silicon-aluminum ratio is 1.5-3.0; preferably, the specific surface area of HY is 550-800m ² /g, and the silicon-aluminum ratio is 2.0-3.0;

The preparation method of the catalyst of the present invention can adopt one or a combination of the precipitation method and the impregnation method to load the active components on the carrier.

The application of the catalyst of the present invention in the reaction of monoethanolamine and ammonia to synthesize ethylenediamine and piperazine under the condition of hydrogen, the reaction conditions are: the reaction temperature is 120-240°C, preferably the reaction temperature is 150-200°C, and the reaction hydrogen pressure is 6.0-12.0 MPa, preferably the hydrogen pressure is 7-10 MPa, the liquid space velocity of monoethanolamine is 0.1-1.0 h ^-1 , preferably the liquid space velocity is 0.3-0.7 h ^-1 .

The catalyst of the present invention is reductively activated under a hydrogen atmosphere before application: the pressure is 0.1-1.0 MPa, preferably the pressure is 0.1-0.5 MPa, the temperature is 200-700 °C, the preferred temperature is 350-600 °C, and the hydrogen space velocity 500-5000h ^-1 , preferably the hydrogen space velocity is 1500-3000h ^-1 .

Compared with the prior art, the catalyst of the invention can significantly reduce the energy consumption of the reaction, increase the conversion rate of monoethanolamine under hydrogen-facing conditions, and simultaneously increase the yield of target products ethylenediamine and piperazine.

Detailed ways

The content of the present invention will be described in detail below.

The catalyst of the present invention is used for the reaction of converting monoethanolamine and ammonia into ethylenediamine and piperazine under the condition of hydrogen. The catalyst consists of three parts: main active component, auxiliary agent and carrier. The main active component is one or several transition metals Ni, Cu or Co, and the auxiliary agent is Fe, Cr, Re, Ru, B, Mg, etc. One or several metals or oxides, and the carrier is H-ZSM-5, H-β, H-MOR or H-Y molecular sieve. The catalyst of the invention is reacted in a fixed-bed reactor, and the reactant monoethanolamine and ammonia can be converted into amine products mainly of ethylenediamine and piperazine with high activity and high selectivity under hydrogen-facing conditions. Specifically, the products are mainly ethylenediamine (EDA) and piperazine (PIP), and diethylenetriamine (DETA), aminoethylpiperazine (AEP), hydroxyethylpiperazine (HEP) and hydroxy Ethylethylenediamine (AEEA), etc.

In the reaction system of the present invention, the mixture of liquid monoethanolamine and ammonia is pumped into a preheater, mixed with hydrogen and preheated to 150° C., and then enters a fixed-bed reactor. Monoethanolamine and ammonia do not need to add any solvent to dissolve and dilute.

In the catalyst of the present invention, the preferred weight percent content of the main active component metal is 1.0-60.0%, the best content is 10.0-25.0%; the preferred weight percentage content of the auxiliary agent is 0.1-30.0%, the best content 1.0-10.0%; the carrier can be H-ZSM-5. The preferred specific surface area is 300-800m ² /g, the optimum specific surface area is 450-600m ² /g, the preferred silicon-aluminum ratio is 10.0-200.0, and the optimum The optimal silicon-aluminum ratio is 50.0-100.0; the carrier can be H-β with a preferred specific surface area of 200-800m ² /g, an optimal specific surface area of 400-700m ² /g, and a preferred silicon-aluminum ratio of 20.0-80.0. The best silicon-aluminum ratio is 40.0-65.0; the carrier can use H-MOR, the best specific surface area is 200-700m ² /g, the best specific surface area is 350-500m ² /g, and the best silicon-aluminum ratio is 5.0-30.0 , the optimal silicon-aluminum ratio is 10.0-20.0; the carrier can be HY with a preferred specific surface area of 300-1000m ² /g, an optimal specific surface area of 550-800m ² /g, and a preferred silicon-aluminum ratio of 1.5-3.0. The optimum silicon-aluminum ratio is 2.0-3.0.

The reaction temperature of the present invention is 160°C, the reaction hydrogen pressure is 8.0MPa, the monoethanolamine liquid volume space velocity is 0.5h ^-1 and the reaction is carried out under the conditions of NH ₃ :MEA:H ₂ =10:1:0.015 (molar ratio) Evaluation. The loading amount of the catalyst is 5ml.

The catalyst of the present invention can be activated by hydrogen treatment under certain conditions before use. The optimal conditions for activating the catalyst with hydrogen are: GHSV=2400h ^-1 , normal pressure, temperature 400°C, and reduction time 4h.

The present invention will be further described below through specific examples.

Example 1

The catalyst is 15%Ni-1.5%Re/H-ZSM-5. Weigh 10 grams of 20-40 mesh H-ZSM-5, dry at 120°C for 4 hours before use, prepare 14ml of an aqueous solution containing 4.672 grams of Ni(NO ₃ ) ₂ , 0.216 grams of NH ₄ ReO ₄ , and use this aqueous solution to impregnate the above H-ZSM-5 carrier, air-dried, oven-treated at 120°C for 4 hours, and baked in a muffle furnace at 500°C for 5 hours. Reductively activate at 390°C in hydrogen (atmospheric pressure, 2400h ^-1 ) for 4 hours before use.

Example 2

The catalyst is 10%Ni-2%Re/H-ZSM-5. Except for preparing 14 ml of an aqueous solution containing 3.114 g of Ni(NO ₃ ) ₂ and 0.288 g of NH ₄ ReO ₄ , other preparation steps were the same as in Example 1.

Example 3

The catalyst is 15%Ni-1.5%Re/H-MOR. Except that 20-40 mesh H-MOR molecular sieves were used instead of H-ZSM-5 molecular sieves, other preparation steps were the same as in Example 1.

Example 4

The catalyst is 15%Ni-1.5%Re/H-Y. Except that 20-40 mesh H-Y molecular sieves were used instead of H-ZSM-5 molecular sieves, other preparation steps were the same as in Example 1.

Example 5

The catalyst is 15%Ni-1.5%Re/H-β. Except that 20-40 mesh H-β molecular sieves were used instead of H-ZSM-5 molecular sieves, other preparation steps were the same as in Example 1.

Example 6

The catalyst is 15%Ni-2%Ru/H-ZSM-5. Except for preparing 14 ml of an aqueous solution containing 4.672 g of Ni(NO ₃ ) ₂ and 0.304 g of RuCl ₃ , other preparation steps were the same as in Example 1.

Example 7

The catalyst is 20%Ni-1%Cr/H-MOR. Except that 20-40 mesh H-MOR molecular sieves are used instead of H-ZSM-5 molecular sieves, and 14ml of an aqueous solution containing 6.229 grams of Ni(NO ₃ ) ₂ and 0.458 grams of Cr(NO ₃ ) ₃ is configured, other preparation steps are the same as in Example 1 .

Example 8

The catalyst is 15%Ni-3.5%Mg/H-MOR. Except that 20-40 mesh H-MOR molecular sieves are used instead of H-ZSM-5 molecular sieves, and 14ml of an aqueous solution containing 4.672 grams of Ni(NO ₃ ) ₂ and 2.132 grams of Mg(NO ₃ ) ₂ is configured, other preparation steps are the same as in Example 1 .

Example 9

The catalyst is 10%Ni-10%Cu-1%B/H-ZSM-5. Except for preparing 14 ml of an aqueous solution containing 3.114 g of Ni(NO ₃ ) ₂ , 2.951 g of Cu(NO ₃ ) ₂ , and 0.572 g of H ₃ BO ₃ , other preparation steps were the same as in Example 1.

Example 10

The catalyst is 25%Co-5%Re/H-MOR. Except that 20-40 mesh H-MOR molecular sieves were used instead of H-ZSM-5 molecular sieves, and 14 ml of an aqueous solution containing 7.766 grams of Co(NO ₃ ) ₂ and 0.720 grams of NH ₄ ReO ₄ were prepared, other preparation steps were the same as in Example 1.

Example 11

The catalyst is 5%Ni-2%Re/H-ZSM-5. Except for preparing 14 ml of an aqueous solution containing 1.557 g of Ni(NO ₃ ) ₂ and 0.288 g of NH ₄ ReO ₄ , other preparation steps were the same as in Example 1.

Example 12

The catalyst is 40%Ni-2%Re/H-ZSM-5. Except for preparing 14 ml of an aqueous solution containing 12.457 grams of Ni(NO ₃ ) ₂ and 0.288 grams of NH ₄ ReO ₄ , other preparation steps were the same as in Example 1.

Example 13

The catalyst is 15%Ni-0.1%Re/H-MOR. Except that 20-40 mesh H-MOR molecular sieves were used instead of H-ZSM-5 molecular sieves, and 14 ml of an aqueous solution containing 4.672 grams of Ni(NO ₃ ) ₂ and 0.014 grams of NH ₄ ReO ₄ was prepared, other preparation steps were the same as in Example 1.

Example 14

The catalyst is 15%Ni-18%Re/HY. Except that 20-40 mesh HY molecular sieves were used instead of H-ZSM-5 molecular sieves, and 14 ml of an aqueous solution containing 4.672 grams of Ni(NO ₃ ) ₂ and 2.593 grams of NH ₄ ReO ₄ was prepared, other preparation steps were the same as in Example 1.

Example 15

The catalyst was 20% Cu-5% Mg/HY. Except that 20-40 mesh HY molecular sieves were used instead of H-ZSM-5 molecular sieves, and 14 ml of an aqueous solution containing 5.903 grams of Cu(NO ₃ ) ₂ and 3.045 grams of Mg(NO ₃ ) ₂ was prepared, other preparation steps were the same as in Example 1.

Example 16

The catalyst is 20%Co-3%Fe/H-MOR. Except that 20-40 mesh H-MOR molecular sieves are used instead of H-ZSM-5 molecular sieves, and 14ml of an aqueous solution containing 6.212 grams of Co(NO ₃ ) ₂ and 1.299 grams of Fe(NO ₃ ) ₃ is configured, other preparation steps are the same as in Example 1 .

The catalyst prepared by the above method is evaluated in a fixed bed reactor, the reaction temperature is 160°C, the hydrogen pressure is 8.0MPa, the liquid volume space velocity of monoethanolamine is 0.5h ^-1 , NH ₃ :MEA:H ₂ =10:1:0.015 (molar ratio), the reaction time was 50 hours. Sampling analysis was carried out by Agilent 7890 gas chromatograph, the chromatographic column was DB-35 capillary chromatographic column, and the detector was hydrogen flame detector. N,N-dimethylformamide (DMFA) was used as an internal standard for quantitative analysis. The results of the reactions are summarized in Table 1.

The conversion rate of the terms monoethanolamine (MEA), ethylenediamine (EDA), piperazine (PIP), diethylenetriamine (DETA), aminoethylpiperazine (AEP), hydroxyethylpiperazine (HEP) in Table 1 ) and the selectivity of hydroxyethylethylenediamine (AEEA) are defined as follows:

Table 1: Catalyst evaluation results for the conversion of monoethanolamine and ammonia to ethylenediamine and piperazine in the presence of hydrogen.

The evaluation results show that: when the weight content of the main active component is in the range of 10.0-25.0%, the conversion rate of monoethanolamine is high; when the weight content of the auxiliary agent is in the range of 1.0-10.0%, the conversion rate of monoethanolamine is high; When used as the main active component or one of the main active components, the catalyst has higher activity; when Re, B, Mg are used as auxiliary agents or one of the auxiliary agents, the catalyst has higher activity; H-ZSM-5 Or when H-Y molecular sieve is used as carrier, it has higher selectivity to ethylenediamine and piperazine; when H-MOR molecular sieve is used as carrier, it has higher selectivity to ethylenediamine; High selectivity.

Claims (7)

1. A catalyst wherein: The catalyst comprises a main active component, an auxiliary agent and a carrier, and the weight of the main active component accounts for 1.0 to 60.0% of the weight of the catalyst, preferably 10.0 to 25.0%; the weight of the auxiliary agent accounts for 0.1 to 30.0% of the weight of the catalyst, preferably 1.0 to 10.0%: The main active component is one or more than two transition metals Ni, Cu or Co, preferably metal Ni; The auxiliary agent is one or more than two kinds of metals or oxides among Fe, Cr, Re, Ru, B, Mg, preferably the auxiliary agents Re, B, Mg; The carrier is H-type molecular sieve. 2. The catalyst according to claim 1, wherein the H-type molecular sieve comprises one or more of H-ZSM-5, H-β, H-MOR or H-Y. 3. The catalyst according to claim 1 or 2, wherein the carrier H-ZSM-5 has a specific surface area of 300-800m ² /g and a silicon-aluminum ratio of 10.0-200.0; The specific surface area of the carrier H-β is 200-800m ² /g, and the silicon-aluminum ratio is 20.0-80.0; The specific surface area of the carrier H-MOR is 200-700m ² /g, and the silicon-aluminum ratio is 5.0-30.0; The specific surface area of the carrier HY is 300-1000 m ² /g, and the silicon-aluminum ratio is 1.5-3.0. 4. A method for preparing a catalyst according to any one of claims 1-3, using one or a combination of precipitation and impregnation to load the active components and auxiliary agents on the carrier. 5. an application of the catalyst described in any one of claims 1-3 in the reaction of monoethanolamine and liquid ammonia to synthesize ethylenediamine and piperazine under hydrogen conditions. 6. The application according to claim 5, characterized in that: the reaction temperature is 120-240°C, the hydrogen reaction pressure is 6.0-12.0MPa, and the monoethanolamine liquid volume space velocity is 0.1-1.0h ^-1 . 7. The application according to claim 5 or 6, wherein the reactor is a fixed bed reactor, and the catalyst is reductively activated under a hydrogen atmosphere before application: the pressure is 0.1-1.0 MPa, the temperature is 200-700 ° C, and the hydrogen The air speed is 500～5000h ^-1 .