CN108465485B - Catalyst for synthesizing triethylene diamine by ethanol amine cyclization and preparation method and application thereof - Google Patents
Catalyst for synthesizing triethylene diamine by ethanol amine cyclization and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for synthesizing triethylene diamine by cyclization of ethanolamine, which comprises an active component and an accelerator, wherein the active component is a TS-1 titanium silicalite molecular sieve; the promoter is strontium oxide (SrO). The content of the accelerant in the catalyst is 1-10 wt%. The catalyst of the invention has simple preparation method and simple operation. In addition, the TS-1 titanium silicalite molecular sieve of the catalyst prepared by the preparation method of the catalyst has better acid center, specific surface area and pore structure, and better catalytic activity. The catalyst of the invention has better ethanolamine conversion rate and triethylene diamine selectivity in the chemical reaction for synthesizing and producing triethylene diamine by taking ethanolamine as a raw material.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a method for synthesizing triethylene diamine (C)6H12N2) In particular to a catalyst prepared from ethanolamine (C)2H7NO) cyclizing to synthesize the triethylene diamine.
Background
Triethylene diamine (TEDA), also known as diazabicyclooctane, or triethylene diamine, is the most widely used tertiary amine foaming catalyst in the polyurethane industry, and a series of products thereof are widely used for various products such as polyurethane soft foams, hard foams, semi-hard foams, elastomers, coatings and the like. According to different raw material routes, there are mainly four synthesis methods, which are respectively: 1. synthetic routes for piperazine and corresponding derivatives; 2. a dichloroethane-ammonia synthesis route; 3. a synthetic route of polyamine compounds by high-temperature deamination; and 4, a hydroxyethyl amine compound dehydration synthetic route.
In the prior art, 1, piperazine and corresponding derivatives are mostly used as raw materials to synthesize TEDA, the method generally has high reaction yield which can reach more than 90%, but the raw materials, particularly the ethyl derivatives of the piperazine, are not easy to obtain, and the cost is high, so that the industrial production of the process is restricted.
Polyamine compound high-temperature deamination reaction takes ethylenediamine polyamine compound as a raw material, the reaction temperature is controlled to be above 320 ℃ under the action of a molecular sieve catalyst, products TEDA and piperazine can be obtained after reaction for a period of time under normal pressure, the products TEDA and piperazine are mainly produced at present, the output ratio of piperazine and TEDA can be adjusted within a certain range through catalyst modification according to market demands, and the piperazine and TEDA co-production multipurpose method is provided.
The dehydration synthesis of TEDA from hydroxyethyl amine compounds is the focus of the current technological research, and the TEDA is obtained by taking hydroxyethyl amine compounds such as ethanolamine, diethanolamine, triethanolamine and the like as raw materials, adding a certain diluent (water, ammonia water, methanol and the like) through the catalytic reaction of an acid catalyst, and dehydrating at high temperature in a fixed bed reactor.
The ethanolamine method was first used by Nippon Kaisha in 1988, and the catalyst used was mainly hydrogen type ZSM-5 molecular sieve, gallium Silicalite (SiO)2/Ge2O375.5) and borosilicate zeolite (SiO)2/B2O3170), taking an aqueous solution of ethanolamine as a raw material, taking hydrogen as a carrier gas, and reacting in a fixed bed reactor to obtain TEDA with the yield of 50-63 percent. Chinese patent CN1182744A discloses a method for synthesizing triethylenediamine (i.e. triethylenediamine in this patent), which adopts a mixture of monoethanolamine and piperazine or monoethanolamine and diethanolamine as a feed material, and adopts hydrogen-type or ammonium-type zeolite treated by a dealuminating agent as a catalyst. The highest conversion rate of monoethanolamine is lower than 72%, and the selectivity of triethylene diamine is lower than 30%. Chinese patent CN104211706A discloses a method for synthesizing triethylene diamine from ethanolamine, wherein methanol or ethanol is used as a solvent, and porous ceramic material loaded with Pt is used as a catalyst to synthesize triethylene diamine in a fixed bed hydrogenation device. The method can reduce reaction temperature and pressure, and improve conversion rate of raw materials. Thus, it can be seen that B is a common herbMost of catalysts for synthesizing triethylene diamine by using alcohol amine are hydrogenation type catalysts.
U.S. Pat. No. 4, 5756741 discloses a synthesis method of triethylene diamine using piperazine and ethylation reagent (ethylenediamine, ethanolamine and polyethylene polyamine, etc.) as raw materials, which adopts a shape-selective zeolite catalyst to obtain triethylene diamine with a total selectivity of 90% through two-step reaction, but the process involves more than two steps of reaction and is complex to operate.
Disclosure of Invention
In view of the above, the present invention is directed to a catalyst for chemical reaction of synthesizing triethylene diamine from ethanolamine.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises an active component and an accelerator, wherein the active component is a TS-1 titanium silicalite molecular sieve, the accelerator is strontium oxide, and the content of the strontium oxide is 1-10 wt% based on the weight of the catalyst.
Further, the content of strontium oxide is 2 to 5 wt%.
The preparation method of the catalyst comprises the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, a template agent and distilled water according to a formula of the solution A, preparing tetrabutyl titanate and isopropanol according to a formula of the solution B, preparing the solution A by using the tetraethyl orthosilicate, the tween 20, the template agent and the distilled water at the temperature of 20-60 ℃, and preparing the solution B by using the tetrabutyl titanate and the isopropanol;
(2) dropwise adding the solution B prepared in the step (1) to the solution A prepared in the step (1) to obtain a mixed solution after the dropwise adding is finished, and standing the mixed solution for 1h to obtain a reaction solution;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle for crystallization, and sequentially performing centrifugation, water washing, alcohol washing, drying and roasting after crystallization to obtain TS-1 raw powder;
(4) preparing strontium chloride and a complexing agent according to the predicted treatment capacity of the TS-1 raw powder in the step (3) in proportion, completely dissolving and stirring the strontium chloride with distilled water to obtain a strontium chloride solution, adding the complexing agent and the TS-1 raw powder in the step (3) into the strontium chloride solution, stirring and absorbing for 1-2 hours at the temperature of 50 ℃, and sequentially carrying out suction filtration, drying and calcination to obtain strontium oxide-loaded TS-1 powder;
(5) and (4) grinding the TS-1 powder obtained in the step (4), adding a binder, tabletting, forming and sieving to obtain the catalyst with the granularity of 30-60 meshes.
Further, in the step (1), the template agent is one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and tetrapropylammonium bromide, and the pH value of the mixed solution in the step (2) is adjusted to be 8-12 by the template agent.
Further, in the step (4), the complexing agent is citric acid and/or tartaric acid.
Further, in the step (5), the binder is carboxymethyl cellulose or sesbania powder, and the addition amount of the binder is 0.1-2 wt% based on the weight part of the catalyst.
Furthermore, the adhesive is sesbania powder, and the addition amount is 0.5-1 wt%.
Further, the TS-1 raw powder in the step (3) has a silicon-titanium ratio of 25-200, wherein silicon is SiO2Calculated as TiO, titanium2And (6) counting.
Further, the silicon-titanium ratio of the TS-1 raw powder in the step (3) is 50-150.
The catalyst is applied to synthesizing triethylene diamine by cyclization of ethanolamine, and the process conditions for synthesizing triethylene diamine by cyclization of ethanolamine are as follows: in a fixed bed reactor, the reaction temperature is 200-400 ℃; the molar ratio of the raw materials ethanolamine, ethanol and water is 1:1-10: 1-20; the liquid space velocity is 1-10h-1Nitrogen is used as carrier gas, and the reaction pressure is 0.1-1 MPa.
After the technical scheme is adopted, the TS-1 titanium silicalite molecular sieve of the catalyst has better acid center, specific surface area and pore structure, so that the catalyst has better catalytic activity.
After the technical scheme is adopted, the preparation method of the catalyst is simple and the operation is simple.
After the technical scheme is adopted, the catalyst provided by the invention has better ethanolamine conversion rate and triethylene diamine selectivity in the chemical reaction for synthesizing and producing triethylene diamine by taking ethanolamine as a raw material.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
First, preparation method
Example 1
The preparation method of the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises the following steps:
(1) tetraethyl orthosilicate, Tween 20, a template agent and distilled water are prepared according to the formula of the solution A, wherein the template agent adopts tetrapropylammonium hydroxide (TPAOH), and tetrabutyl titanate (TBOT) and isopropanol are prepared according to the formula of the solution B. Preparing tetraethyl orthosilicate, Tween 20, tetrapropylammonium hydroxide (TPAOH) and distilled water into solution A at 25 ℃, wherein the molar ratio of tetraethyl orthosilicate to Tween 20 to TPAOH to distilled water in the solution A is 1: 0.03: 0.2: 50; preparing solution B from isopropanol and tetrabutyl titanate, wherein the molar ratio of TBOT to isopropanol in the solution B is 1: 5-10;
in the present invention, tetraethyl orthosilicate is SiO in the molar ratio of the amounts of raw materials charged2Tetrabutyl titanate in TiO2In this example, the molar ratio of the raw materials to SiO2：TiO2＝1:0.01。
(2) Slowly dripping the liquid B prepared in the step (1) into the liquid A prepared in the step (1), controlling the dripping speed to be 5-6 s/drop, completely dripping the liquid B into the liquid A to obtain a mixed liquid, and reacting the mixed liquid for 1h to obtain a reaction liquid; wherein, the template agent (TPAOH) of the solution A not only plays the function of the template agent, but also can be used as an alkali source to adjust the pH value of the mixed solution, and the pH value range of the mixed solution is 8-12;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle, crystallizing at 170 ℃ for 24 hours to finish crystallization, sequentially centrifuging, washing with water, washing with alcohol, drying at 50 ℃ for 24 hours, and calcining at 550 ℃ for 5 hours to obtain TS-1(100-a) raw powder, wherein in the example, in the TS-1(100-a) expression, 100 represents the silicon-titanium ratio, and a represents that the template agent is tetrapropylammonium hydroxide. In the present invention, the silicon-titanium ratio of the TS-1 raw powder is 25 to 200, preferably 50 to 150, for example, the silicon-titanium ratio of the present embodiment is 100.
(4) According to the predicted treatment amount of the TS-1(100-a) raw powder in the step (3), preparing strontium chloride and a complexing agent in proportion, wherein the complexing agent is citric acid, the following description is given by taking 1g of the TS-1(100-a) raw powder as an example, weighing 0.015g of the strontium chloride to dissolve in distilled water, stirring for 30min, pouring 1g of the TS-1(100-a) raw powder and 0.05g of the citric acid into a strontium chloride solution, stirring and absorbing at 50 ℃ for 1-2h, sequentially performing suction filtration, drying at 100 ℃ for 8h, and calcining at 500 ℃ for 2h to obtain 1% strontium oxide-loaded TS-1(100-a) powder;
(5) and (3) grinding the TS-1(100-a) powder obtained in the step (4) to the granularity of less than 200 meshes, adding sesbania powder, tabletting and forming, and sieving to obtain the 30-60-mesh 1% SrO/TS-1(100-a-CA) catalyst, wherein 0.5 wt% of sesbania powder is added in the catalyst according to the parts by weight of the catalyst. In the expression of 1% SrO/TS-1(100-a-CA), CA represents that the complexing agent is citric acid.
The 1% SrO/TS-1(100-a-CA) catalyst is used for chemical reaction for synthesizing triethylene diamine through ethanol amine cyclization.
Example 2
The preparation method of the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, tetrapropylammonium hydroxide (TPAOH) and distilled water into solution A and preparing isopropanol and tetrabutyl titanate into solution B at 25 ℃; in this example, the molar ratio of the amount of raw materials charged to SiO2：TiO2：TPAOH＝1:0.01:0.2；
(2) Slowly dripping the liquid B prepared in the step (1) into the liquid A prepared in the step (1), controlling the dripping speed to be 5-6 s/drop, completely dripping the liquid B into the liquid A, and reacting for 1h to obtain a reaction liquid;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle, crystallizing at 170 ℃ for 24 hours to finish crystallization, and sequentially centrifuging, washing with water, washing with alcohol, drying at 50 ℃ for 24 hours, and calcining at 550 ℃ for 5 hours to obtain TS-1(100-a) raw powder;
(4) weighing 0.075g of strontium chloride, dissolving the strontium chloride with distilled water, stirring for 30min, pouring 1g of TS-1(100-a) raw powder and 0.05g of citric acid into a strontium chloride solution, stirring and absorbing at 50 ℃ for 1-2h, sequentially performing suction filtration, drying at 100 ℃ for 8h, and calcining at 500 ℃ for 2h to obtain 5% strontium oxide loaded TS-1(100-a-CA) powder;
(5) and (3) grinding the TS-1(100-a-CA) powder obtained in the step (4), adding sesbania powder, tabletting, forming and sieving to obtain the 5% SrO/TS-1(100-a-CA) catalyst with the granularity of 30-60 meshes, wherein 0.5 wt% of sesbania powder is added in the catalyst according to the weight part of the catalyst.
The 5% SrO/TS-1(100-a-CA) catalyst is used for chemical reaction for synthesizing triethylene diamine through ethanol amine cyclization.
Example 3
The preparation method of the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, tetrapropylammonium hydroxide (TPAOH) and distilled water into solution A and preparing isopropanol and tetrabutyl titanate into solution B at 25 ℃; in this example, the molar ratio of the raw materials to SiO2：TiO2：TPAOH＝1:0.01:0.2；
(2) Slowly dripping the liquid B prepared in the step (1) into the liquid A prepared in the step (1), controlling the dripping speed to be 5-6 s/drop, completely dripping the liquid B into the liquid A, and reacting for 1h to obtain a reaction liquid;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle, crystallizing at 170 ℃ for 24 hours to finish crystallization, and sequentially centrifuging, washing with water, washing with alcohol, drying at 50 ℃ for 24 hours, and calcining at 550 ℃ for 5 hours to obtain TS-1(100-a) raw powder;
(4) in the embodiment, the complexing agent is tartaric acid, specifically, 0.075g of strontium chloride is weighed and dissolved in distilled water, the solution is stirred for 30min, 1g of TS-1(100-a) raw powder and 0.05g of tartaric acid are poured into a strontium chloride solution, the solution is stirred and absorbed for 1-2h at 50 ℃, and TS-1(100-a-TA) powder loaded with 5% of strontium oxide is obtained after the solution is sequentially subjected to suction filtration, drying at 100 ℃ for 8h and calcining at 500 ℃ for 2 h;
(5) and (3) grinding the TS-1(100-a-TA) powder obtained in the step (4), adding sesbania powder, tabletting, forming and sieving to obtain the 5% SrO/TS-1(100-a-TA) catalyst with the granularity of 30-60 meshes, wherein 0.5 wt% of sesbania powder is added in the catalyst according to the weight part of the catalyst. In the expression of 5% SrO/TS-1(100-a-TA), TA represents tartaric acid.
The 5% SrO/TS-1(100-a-TA) catalyst is used for chemical reaction for synthesizing triethylene diamine through ethanol amine cyclization.
Example 4
The preparation method of the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, tetrapropylammonium hydroxide (TPAOH) and distilled water into solution A and preparing isopropanol and tetrabutyl titanate into solution B at 25 ℃; in this example, the molar ratio of the raw materials to SiO2：TiO2：TPAOH＝1:0.01:0.2；
(2) Slowly dripping the liquid B prepared in the step (1) into the liquid A prepared in the step (1), controlling the dripping speed to be 5-6 s/drop, completely dripping the liquid B into the liquid A, and reacting for 1h to obtain a reaction liquid;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle, crystallizing at 170 ℃ for 24 hours to finish crystallization, and sequentially centrifuging, washing with water, washing with alcohol, drying at 50 ℃ for 24 hours, and calcining at 550 ℃ for 5 hours to obtain TS-1(100-a) raw powder;
(4) weighing 0.15g of strontium chloride, dissolving the strontium chloride with distilled water, stirring for 30min, pouring 1g of TS-1(100-a) raw powder and 0.05g of citric acid into a strontium chloride solution, stirring and absorbing at 50 ℃ for 1-2h, sequentially performing suction filtration, drying at 100 ℃ for 8h, and calcining at 500 ℃ for 2h to obtain TS-1(100-a-CA) powder loaded with 10% strontium oxide;
(5) and (3) grinding the TS-1(100-a-CA) powder obtained in the step (4), adding sesbania powder, tabletting, forming and sieving to obtain the 10% SrO/TS-1(100-a-CA) catalyst with the granularity of 30-60 meshes, wherein 0.5 wt% of sesbania powder is added in the catalyst according to the weight part of the catalyst.
The 10% SrO/TS-1(100-a-CA) catalyst is used for the chemical reaction of synthesizing triethylene diamine by cyclization of ethanolamine.
It should be noted that:
1. the catalyst for synthesizing triethylene diamine by cyclization of ethanolamine prepared in the above examples 1 to 4 comprises an active component and a promoter, wherein the active component is a TS-1 titanium silicalite molecular sieve, the promoter is strontium oxide (SrO), and the content of the strontium oxide is 1 to 10 wt%, preferably 2 to 5 wt%, based on the weight part of the catalyst. The prepared TS-1 titanium silicalite molecular sieve has a good acid center, a specific surface area and a pore structure, and has good catalytic activity.
2. In examples 1 to 4, the templating agent may be one or more of tetrabutylammonium hydroxide and tetrapropylammonium bromide, in addition to the tetrapropylammonium hydroxide (TPAOH) described above;
3. in examples 1 to 4, carboxymethyl cellulose may be used as the binder in addition to the sesbania powder. In the catalyst, the addition amount of the binder is controlled to be 0.1-2 wt% according to different types of binders, and when the binder is sesbania powder, the addition amount of the sesbania powder is controlled to be 0.5-1 wt%.
4. In examples 2 to 4, the same formulations as those of the solutions A and B of example 1 were used.
Example 5
The preparation method of the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises the following steps:
(1) tetraethyl orthosilicate (TEOS), Tween 20, a template and distilled water are prepared according to the formula of the solution A, wherein the template adopts tetrapropylammonium hydroxide (TPAOH), and tetrabutyl titanate (TBOT) and isopropanol are prepared according to the formula of the solution B. Preparing tetraethyl orthosilicate, tween 20, tetrapropylammonium hydroxide (TPAOH) and distilled water into solution A, and preparing isopropanol and tetrabutyl titanate into solution B at 25 ℃; in this example, the molar ratio of the raw materials of the catalyst to SiO2：TiO2：TPAOH＝1:0.01:0.2。
(2) Slowly dripping the liquid B prepared in the step (1) into the liquid A prepared in the step (1), controlling the dripping speed to be 5-6 s/drop, completely dripping the liquid B into the liquid A, and reacting for 1h to obtain a reaction liquid;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle, crystallizing at 170 ℃ for 24 hours to finish crystallization, and sequentially centrifuging, washing with water, washing with alcohol, drying at 50 ℃ for 24 hours, and calcining at 550 ℃ for 5 hours to obtain TS-1(100-a) raw powder;
further, grinding the TS-1(100-a) raw powder obtained in the step (3), adding a binder, tabletting and forming the binder by using sesbania powder, and sieving to obtain the TS-1(100-a) catalyst with 30-60 meshes, wherein the catalyst contains 0.5 wt% of sesbania powder in parts by weight.
Example 6
The preparation method of the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, tetrapropylammonium hydroxide (TPAOH) and distilled water into solution A and preparing isopropanol and tetrabutyl titanate into solution B at 25 ℃; in this example, the molar ratio of the raw materials to SiO2：TiO2：TPAOH＝1:0.008:0.2；
(2) Slowly dripping the liquid B prepared in the step (1) into the liquid A prepared in the step (1), controlling the dripping speed to be 5-6 s/drop, completely dripping the liquid B into the liquid A, and reacting for 1h to obtain a reaction liquid;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle, crystallizing at 170 ℃ for 24 hours to finish crystallization, sequentially centrifuging, washing with water, washing with alcohol, drying at 50 ℃ for 24 hours, calcining at 550 ℃ for 5 hours to obtain TS-1(125-a) raw powder,
further, grinding the TS-1(125-a) raw powder, adding sesbania powder, tabletting, forming and sieving to obtain the TS-1(125-a) catalyst with 30-60 meshes, wherein the weight of the catalyst is 0.5 wt% of the sesbania powder.
Example 7
The preparation method of the catalyst for synthesizing triethylene diamine by ethanol amine cyclization comprises the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, tetrabutylammonium hydroxide (TBAOH) and distilled water into solution A at 25 ℃, and preparing isopropanol and tetrabutyl titanate into solution B; in this example, the molar ratio of the raw materials to SiO2：TiO2：TBAOH＝1:0.01:0.2；
(2) Slowly dripping the liquid B prepared in the step (1) into the liquid A prepared in the step (1), controlling the dripping speed to be 5-6 s/drop, completely dripping the liquid B into the liquid A, and reacting for 1h to obtain a reaction liquid;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle, crystallizing at 170 ℃ for 24 hours to finish crystallization, sequentially centrifuging, washing with water, washing with alcohol, drying at 50 ℃ for 24 hours, and calcining at 550 ℃ for 5 hours to obtain TS-1(100-b) raw powder, wherein in the example, in the TS-1(100-b) expression, 100 represents a silicon-titanium ratio, and b represents that a template agent is tetrabutylammonium hydroxide, so that the method is convenient to distinguish from the template agent a in the example 1;
further, grinding the TS-1(100-b) raw powder, adding sesbania powder, tabletting, forming and sieving to obtain the TS-1(100-b) catalyst with 30-60 meshes, wherein the catalyst contains 0.5 wt% of the sesbania powder in parts by weight.
In examples 5 to 7, the same formulations as those of the solutions a and B in example 1 were used for the formulations of the solutions a and B. The catalysts prepared in examples 5-7 above, having an active component which is a TS-1 titanium silicalite, operated without supporting strontium oxide, as compared to the catalysts of examples 1-4, thus the catalysts of examples 5-7 do not have strontium oxide, i.e., no promoter.
Second, evaluation of Activity
The catalysts prepared in the above examples 1 to 7 were applied to chemical reactions for synthesizing triethylene diamine by cyclization of ethanolamine, and activity evaluation was performed by the following method: the method is carried out on a miniature fixed bed reactor, the filling amount of the catalyst is 1mL, and the reaction temperature of the catalyst is 250-350 ℃; nitrogen is used as carrier gas, and the reaction pressure is 0.2 MPa; the mol ratio of the ethanol to the distilled water of the raw material ethanolamine is 1:2:3, and the liquid space velocity is 3h-1. After reacting for 2h, the reaction tail gas is automatically sampled by a ten-way valve, and gas chromatography is introduced for on-line analysis. A chromatographic column: OV-101; column length: 30 m; pipe diameter: Φ 0.32mm, hydrogen flame detector (FID), column temperature: 170 ℃, detector temperature: 230 ℃, injector temperature: at 200 ℃.
The results of activity evaluation of the catalysts of examples 1 to 7 are shown in Table 1. Examples 1 to 4 are experimental groups, and the catalyst comprises an active component (TS-1 titanium silicalite) and a promoter (strontium oxide); examples 5-7 are control groups, the catalyst includes an active component (TS-1 titanium silicalite).
Table 1 catalyst composition and activity evaluation results of examples
*XMEATo ethanolamine conversion; sTEDASelectivity to triethylenediamine.
As can be seen from the table above, the catalyst of the invention has better ethanolamine conversion rate and triethylene diamine selectivity in the chemical reaction for synthesizing and producing triethylene diamine by taking ethanolamine as a raw material, namely the catalyst has better catalytic activity, and the ethanolamine conversion rate is intensively kept between 45% and 55%, and can reach 58.11% at most; the selectivity of triethylene diamine is intensively maintained between 60 and 70 percent, and can reach 72.71 percent at most, in addition, the catalytic activity of the catalyst containing strontium oxide (examples 1 to 4) is obviously higher than that of the catalyst not containing strontium oxide (examples 5 to 7), and the catalyst with the strontium oxide content of 5 weight percent has better ethanolamine conversion rate and triethylene diamine selectivity. It can be seen that the catalyst containing strontium oxide has a good catalytic activity, and the content of strontium oxide in the catalyst is preferably 5 wt%.
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (10)
1. The catalyst for synthesizing triethylene diamine by ethanol amine cyclization is characterized in that: the catalyst comprises an active component and an accelerant, wherein the active component is a TS-1 titanium silicalite molecular sieve, the accelerant is strontium oxide, and the content of the strontium oxide is 1-10 wt% based on the weight of the catalyst;
the preparation method of the catalyst comprises the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, a template agent and distilled water according to a formula of the solution A, preparing tetrabutyl titanate and isopropanol according to a formula of the solution B, preparing the solution A by using the tetraethyl orthosilicate, the tween 20, the template agent and the distilled water at the temperature of 20-60 ℃, and preparing the solution B by using the tetrabutyl titanate and the isopropanol;
(2) dropwise adding the solution B prepared in the step (1) to the solution A prepared in the step (1) to obtain a mixed solution after the dropwise adding is finished, and standing the mixed solution for 1h to obtain a reaction solution;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle for crystallization, and sequentially performing centrifugation, water washing, alcohol washing, drying and roasting after crystallization to obtain TS-1 raw powder;
(4) preparing strontium chloride and a complexing agent according to the predicted treatment capacity of the TS-1 raw powder in the step (3) in proportion, completely dissolving and stirring the strontium chloride with distilled water to obtain a strontium chloride solution, adding the complexing agent and the TS-1 raw powder in the step (3) into the strontium chloride solution, stirring and absorbing for 1-2 hours at the temperature of 50 ℃, and sequentially carrying out suction filtration, drying and calcination to obtain strontium oxide-loaded TS-1 powder;
(5) and (4) grinding the TS-1 powder obtained in the step (4), adding a binder, tabletting, forming and sieving to obtain the catalyst with the granularity of 30-60 meshes.
2. The catalyst for the cyclization of triethylenediamine with ethanolamine according to claim 1, wherein: the content of strontium oxide is 2-5 wt%.
3. The preparation method of the catalyst for synthesizing triethylene diamine by cyclization of ethanolamine is characterized by comprising the following steps:
(1) preparing tetraethyl orthosilicate, tween 20, a template agent and distilled water according to a formula of the solution A, preparing tetrabutyl titanate and isopropanol according to a formula of the solution B, preparing the solution A by using the tetraethyl orthosilicate, the tween 20, the template agent and the distilled water at the temperature of 20-60 ℃, and preparing the solution B by using the tetrabutyl titanate and the isopropanol;
(2) dropwise adding the solution B prepared in the step (1) to the solution A prepared in the step (1) to obtain a mixed solution after the dropwise adding is finished, and standing the mixed solution for 1h to obtain a reaction solution;
(3) transferring the reaction liquid obtained in the step (2) to a hydrothermal kettle for crystallization, and sequentially performing centrifugation, water washing, alcohol washing, drying and roasting after crystallization to obtain TS-1 raw powder;
(4) preparing strontium chloride and a complexing agent according to the predicted treatment capacity of the TS-1 raw powder in the step (3) in proportion, completely dissolving and stirring the strontium chloride with distilled water to obtain a strontium chloride solution, adding the complexing agent and the TS-1 raw powder in the step (3) into the strontium chloride solution, stirring and absorbing for 1-2 hours at the temperature of 50 ℃, and sequentially carrying out suction filtration, drying and calcination to obtain strontium oxide-loaded TS-1 powder;
(5) and (4) grinding the TS-1 powder obtained in the step (4), adding a binder, tabletting, forming and sieving to obtain the catalyst with the granularity of 30-60 meshes.
4. The method of claim 3, wherein: in the step (1), the template agent is one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and tetrapropylammonium bromide, and the pH value of the mixed solution in the step (2) is adjusted to be 8-12 by the template agent.
5. The method of claim 3, wherein: in step (4), the complexing agent is citric acid and/or tartaric acid.
6. The method of claim 3, wherein: in the step (5), the binder is carboxymethyl cellulose or sesbania powder, and the addition amount of the binder is 0.1-2% by weight of the catalyst.
7. The method of claim 6, wherein: the adhesive is sesbania powder, and the addition amount is 0.5-1%.
8. The method of claim 3, wherein: the silicon-titanium ratio of the TS-1 raw powder in the step (3) is 25-200, wherein the silicon is SiO2Calculated as TiO, titanium2And (6) counting.
9. The method of claim 8, wherein: the silicon-titanium ratio of the TS-1 raw powder in the step (3) is 50-150.
10. The application of the catalyst as claimed in claim 1 or 2, wherein the catalyst is applied to the synthesis of triethylene diamine by cyclization of ethanolamine, and the process conditions of the synthesis of triethylene diamine by cyclization of ethanolamine are as follows: in a fixed bed reactor, the reaction temperature is 200-400 ℃; the molar ratio of the raw materials ethanolamine, ethanol and water is 1:1-10: 1-20; the liquid space velocity is 1-10h-1Nitrogen is used as carrier gas, and the reaction pressure is 0.1-1 MPa.
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