Method for mainly producing triethylenediamine and concurrently producing functional foaming catalyst from triethanolamine

Abstract

The present invention belongs to the field of chemical industry, and discloses a method for mainly producing triethylenediamine and concurrently producing a functional foaming catalyst from triethanolamine, comprising the following steps: step 1, using an aqueous solution of triethanolamine and a nitrogen source substance as a raw material liquid, reacting in a fixed bed reactor loaded with a solid acid catalyst, and subjecting the reaction product to distillation separation to obtain triethylenediamine, a light component, and a heavy component as a product, respectively; step 2, preparing a functional foaming catalyst by compounding the heavy component. The present invention proposes for the first time to use triethanolamine as an initial raw material, and urea, ammonium carbonate, ammonium bicarbonate, ammonia and other nitrogen source substances as a reaction nitrogen source, with simple raw materials, wide sources, low cost, and no azeotropy with the product, and conventional distillation is sufficient for the post-treatment of the crude product, and the operation is simple.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, and particularly relates to a method for mainly producing triethylenediamine and concurrently producing a functional foaming catalyst from triethanolamine. Background Art

[0002] Triethylenediamine (TEDA for short), CAS No. 280-57-9, molecular formula C6H 12 N2, referred to as TEDA, has a structural formula as shown in Formula 1. It is the most widely used and largest amount of tertiary amine foaming catalyst in the polyurethane industry. Its series of products are widely used in various products such as polyurethane soft foam, rigid foam, semi-rigid foam, elastomer and coating. In addition, TEDA can also be used as a catalyst for olefin polymerization, epoxide and resin, and its derivatives can also be used in plastics, agriculture and electroplating industries, etc., with a wide range of uses.

[0003]

[0004] There are many methods for synthesizing TEDA at home and abroad. According to the type of raw materials, there are mainly the following processes:

[0005] (1) A synthesis process using piperazine and its derivatives (N-hydroxyethylpiperazine, N,N-dihydroxyethylpiperazine, N-aminoethylpiperazine, etc.) as raw materials and HZSM-5 molecular sieve as catalyst; this process is described in detail in patents such as USP20020072467, USP6350874, and CN1182744A; this process is mature and the yield of TEDA is high, but piperazine and its derivatives are limited in resources and expensive, which restricts this method.

[0006] (2) Synthesis process of co-producing piperazine and TEDA using ethylenediamine as raw material; CN105080595A, CN104888844A, CN102600884A and CN106831794B all reported methods of using ethylenediamine as raw material to produce PIP and co-produce high-value TEDA. Currently, the product is mainly piperazine. Although the output ratio of piperazine and TEDA can be adjusted within a certain range by modifying the catalyst, the selectivity of TEDA is poor. Ethylenediamine is relatively expensive and belongs to explosive chemicals. The industrial production cost is high and the output is low, making this method unable to meet the increasing market demand.

[0007] (3) A synthesis process for synthesizing TEDA using monoethanolamine as a raw material or a mixed alcohol amine of monoethanolamine and diethanolamine as a raw material; the ethanolamine method was first used by Idemitsu Kosan Co., Ltd. of Japan in 1988, and the catalysts used were mainly hydrogen-type ZSM-5 molecular sieves, gallium silicate zeolite and boron zeolite, etc., but this method has a low yield and high energy consumption. CN1182744A discloses a synthesis method for TEDA, using a mixture of monoethanolamine and piperazine or monoethanolamine and diethanolamine as a feed, and using hydrogen-type or ammonium-type zeolite treated with a dealuminant as a catalyst. However, the selectivity of TEDA is low. Due to the low cost of raw materials in this process, it has become a hot research direction for synthesizing TEDA, and has been widely studied and optimized in patents such as CN101735224A, CN1197865C, CN108465485B, and CN104211706B. However, as described in patents CN102584833B, CN104628675B, and CN103012412B, since the boiling points of TEDA (boiling point of 174°C) and ethanolamine (boiling point of 170°C) are very close, the two easily form azeotropes, and conventional distillation is difficult to separate the two. The product needs to undergo a complex post-processing process to obtain a TEDA product of qualified purity, which greatly increases production efficiency and cost.

[0008] The current TEDA synthesis method has problems such as high raw material cost, poor selectivity, great separation difficulty, and low target product production capacity. There is an urgent need for a new TEDA synthesis route with low cost, high production capacity, and suitable for large-scale industrial production. Summary of the invention

[0009] The technical problem to be solved by the present invention is to provide a new method for synthesizing TEDA using triethanolamine as a raw material at a low cost, that is, a method for mainly producing triethylenediamine and concurrently producing a functional foaming catalyst from triethanolamine.

[0010] In order to solve the above technical problems, the present invention provides a method for mainly producing triethylenediamine and concurrently producing a functional foaming catalyst from triethanolamine, comprising the following steps:

[0011] Step 1: using an aqueous solution of triethanolamine and a nitrogen source as a raw material liquid, reacting in a fixed bed reactor loaded with a solid acid catalyst, the pressure of the fixed bed reactor is 0-0.5 MPa (preferably 0.1-0.4 MPa), the temperature is 300-400° C. (preferably 320-390° C.), and the feed weight hourly space velocity of the raw material liquid is 0.2-2 / h (preferably 0.8-1.5 / h);

[0012] The molar ratio of nitrogen atoms in the nitrogen source to triethanolamine is 0 to 4.0:1 (preferably 1 to 3:1);

[0013] The product obtained from the reaction (TEDA crude product) is subjected to distillation separation to obtain triethylenediamine, light components and heavy components as products, respectively. The heavy components are used for compounding to prepare a functional foaming catalyst.

[0014] As an improvement to the method of the present invention, the light component is recycled as a reaction raw material.

[0015] Note: When the light component is recovered and recycled, it is used to replace 20±5% by weight of the nitrogen source substance aqueous solution.

[0016] As a further improvement of the method of the present invention:

[0017] It also includes the following step 2:

[0018] Step 2: Preparation of functional foaming catalyst (preparation of functional foaming catalyst by compounding heavy components):

[0019] The raw materials of the functional foaming catalyst are composed of the following components by weight: 5% to 15% of heavy components, 25% to 35% of amine catalyst A33 (triethylenediamine A-33 amine catalyst), 25% to 35% of dipropylene glycol (dipropylene glycol), 5% to 15% of PPG-2000 (hydroxyl value: 51 to 62 mgKOH / g), and 20% to 30% of bis(dimethylamino)ethyl ether;

[0020] The heavy component, amine catalyst A33, dipropylene glycol, and PPG-2000 are added to a container (such as a three-necked flask), heated to 60±10°C under the protection of an inert gas (such as nitrogen), stirred continuously for 2±0.5h, cooled to room temperature, and then bis(dimethylamino)ethyl ether is added, and high-speed stirring (about 1500rad / min) is continued at room temperature for 1±0.5h to obtain a functional foaming catalyst.

[0021] As a further improvement of the method of the present invention: the step 1 comprises the following steps:

[0022] 1) Loading a solid acid catalyst into a fixed bed catalytic reactor;

[0023] 2) Stirring the aqueous solution of triethanolamine and nitrogen source at room temperature to form a raw material liquid, and then injecting the raw material liquid at a uniform speed by using an injection pump. After the raw material liquid is vaporized in a vaporization chamber (350° C.), a continuous amination reaction is carried out by a solid acid catalyst in a reactor. The feed weight hourly space velocity of the raw material liquid (the liquid weight hourly space velocity of the raw material liquid) is 0.2 to 2 / h (preferably 0.8 to 1.5 / h), the reaction pressure is 0 to 0.5 MPa (preferably 0.1 to 0.4 MPa), and the temperature is 300 to 400° C. (preferably 320 to 390° C.);

[0024] Weight hourly space velocity = feed weight of raw material liquid per hour / loading weight of solid acid catalyst;

[0025] 3) The reaction liquid obtained in step 2) is collected by condensing through a condenser, and subjected to atmospheric distillation in a distillation kettle. The fraction collected at 10 to 130° C. is the light component (recovery and recycling); the fraction collected at 130 to 175° C. is the TEDA fraction, and the remaining fraction in the distillation kettle is the heavy component.

[0026] Note: When the light component is recycled, it is used to replace 20±5% by weight of the nitrogen source aqueous solution;

[0027] The TEDA fraction needs to be distilled twice to obtain qualified TEDA products.

[0028] As a further improvement of the method of the present invention: the nitrogen source substance is a substance that can decompose into ammonia, including urea, ammonium carbonate, ammonium bicarbonate, and ammonia.

[0029] As a further improvement of the method of the present invention: the aqueous solution of the nitrogen source substance is preferably a saturated aqueous solution of the nitrogen source substance.

[0030] As a further improvement of the method of the present invention: the preparation method of the solid acid catalyst is:

[0031] Aluminum sol as a carrier and active components (dried and fully ground active components) are mixed evenly (mixed evenly in a planetary mixer) to form a catalyst raw material;

[0032] The catalyst raw material is first extruded by a twin-screw extruder at room temperature, then calcined by a programmed temperature rise method, and then naturally cooled to room temperature to obtain a solid acid catalyst;

[0033] The active component is at least one of the following phosphates (i.e., any one of 1 to 5): strontium hydrogen phosphate, zirconium hydrogen phosphate, barium hydrogen phosphate, calcium hydrogen phosphate, and magnesium hydrogen phosphate;

[0034] The active component accounts for 80-95% of the total weight of the catalyst raw material; the carrier accounts for 5-20% of the total weight of the catalyst raw material.

[0035] Note: Aluminum sol is a conventional commercial product, and the weight content of aluminum oxide in the aluminum sol is about 23%.

[0036] The solid acid catalyst is cylindrical with a diameter of 3 to 6 mm and a length of 5 to 10 mm.

[0037] As a further improvement of the method of the present invention: the programmed temperature in the preparation method of the solid acid catalyst is: calcination at 100±10℃ for 30±5min, calcination at 150±10℃ for 30±5min, calcination at 200±10℃ for 30±5min, calcination at 300±10℃ for 60±5min, calcination at 400±10℃ for 60±5min, calcination at 500±10℃ for 60±5min, calcination at 600±10℃ for 120±5min, and calcination at 700±10℃ for 180±5min.

[0038] As a further improvement of the method of the present invention: the active component is composed of the following ingredients in parts by weight: 60-90 parts of strontium hydrogen phosphate, 5-20 parts of zirconium hydrogen phosphate, 5-10 parts of barium hydrogen phosphate, 0-5 parts of calcium hydrogen phosphate, and 0-5 parts of magnesium hydrogen phosphate.

[0039] As a further improvement of the method of the present invention: the active component is composed of the following components by weight: 60g strontium hydrogen phosphate, 20g zirconium hydrogen phosphate, 10g barium hydrogen phosphate, 5g calcium hydrogen phosphate, and 5g magnesium hydrogen phosphate;

[0040] The amount of aluminum sol is 20 g.

[0041] In the present invention, the main reaction formula for synthesizing TEDA using triethanolamine (TEA) and a nitrogen source as an example is:

[0042]

[0043] The reason why the prior art has not found the use of triethanolamine as a raw material to synthesize triethylenediamine is that triethanolamine as a raw material will theoretically generate TEDA in one step with ammonia, but under the action of a catalyst, triethanolamine may undergo etherification, cracking and other reactions at high temperatures, resulting in a low yield of the main product. In addition, the water content in the system has a greater impact on the by-products in such reactions (source reference to the results described in the literature using ethanolamine as a raw material).

[0044] The present invention improves the above problems from the following perspectives:

[0045] (1) A relatively mildly active solid acid catalyst is used as a reaction raw material, and the type and content of by-products are effectively reduced by controlling process parameters such as temperature, pressure, and space velocity, so that the main by-products are controlled to be light components of morpholine (mainly including morpholine and its derivatives) and heavy components of morpholine ethanol (mainly including morpholine ethanol and its derivatives) with practical value, wherein the light components of morpholine can replace nitrogen sources as raw materials, and the heavy components of morpholine ethanol are compounded into a foaming catalyst.

[0046] (2) Use aqueous solutions of urea, ammonium carbonate, and ammonium bicarbonate instead of aqueous ammonia. On the one hand, the endothermic reaction of urea, ammonium carbonate, ammonium bicarbonate and other substances to decompose and produce ammonia gas can be used to make the actual reaction more gentle and controllable. On the other hand, urea, ammonium carbonate, ammonium bicarbonate and other substances have high solubility in water (ammonia water can be configured to a maximum of 28% saturated solution, and urea can be configured to a maximum of 48% saturated solution), which can reduce the discharge of wastewater and effectively control by-products.

[0047] (3) By using a suitable catalyst, in combination with the corresponding synthesis device, method and separation conditions, a high-yield TEDA fraction can be obtained. At the same time, the separated light components can be applied, and the heavy components can be compounded into a catalyst for use, so that the by-products can be comprehensively utilized, which is economical and environmentally friendly.

[0048] The present invention develops a method for producing triethylenediamine and a functional foaming catalyst using triethanolamine and a nitrogen source as main raw materials, which has the following technical advantages:

[0049] (1) It is the first time to propose the use of triethanolamine as the initial raw material and urea, ammonium carbonate, ammonium bicarbonate, ammonia and other nitrogen sources as the reaction nitrogen source. The raw materials are simple, widely available, low cost, and do not azeotrope with the product. The crude product can be post-treated by conventional distillation, and the operation is simple;

[0050] (2) Using self-made non-precious metal solid acid as a catalyst not only effectively controls the reaction activity, but also reduces the types and contents of by-products. By-products are simple and easy to handle, and the cost is lower;

[0051] (3) Separation and comprehensive utilization of TEDA crude product, wherein the separated light component is recycled to produce TEDA, and the heavy component is compounded into a functional foaming catalyst. This process has a high raw material utilization rate, less waste, and is easy to industrialize and mass produce.

[0052] (4) Compared with the mixture of monoethanolamine and diethanolamine as the raw material, the advantages of the present invention are: the raw material triethanolamine is simple, widely available, low cost, and does not form an azeotrope with the product, and the conventional distillation post-treatment operation is simple.

[0053] Compared with "diethanolamine" as a raw material, the advantages of the present invention are: the raw material triethanolamine is simple, widely available, low cost, and the types and contents of by-products in the obtained TEDA crude product are relatively small. DETAILED DESCRIPTION

[0054] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0055] The aluminum sol is a conventional commercial product. The weight content of aluminum oxide in the aluminum sol is about 23%, and the pH value is 3.

[0056] Catalyst Example 1, Preparation of Catalyst A:

[0057] The active components consist of 60g of strontium hydrogen phosphate, 20g of zirconium hydrogen phosphate, 10g of barium hydrogen phosphate, 5g of calcium hydrogen phosphate and 5g of magnesium hydrogen phosphate; aluminum sol as a carrier and the active components are combined into a catalyst raw material.

[0058] Follow these steps in order:

[0059] ①. Dry 60 g of commercially available strontium hydrogen phosphate, 20 g of zirconium hydrogen phosphate, 10 g of barium hydrogen phosphate, 5 g of calcium hydrogen phosphate and 5 g of magnesium hydrogen phosphate in a vacuum oven at 120°C for 3 h, cool to room temperature, and then grind them conventionally using a ball mill to obtain a solid powder (passed through a 100-mesh sieve).

[0060] ② Add 20 g of aluminum sol to the solid powder obtained in step ①, stir it mechanically, add it to a double planetary mixer, stir it at room temperature and vacuum high speed (speed of about 1500-2500 rad / min) for 30 minutes, transfer it to a twin-screw extruder after mixing, and extrude it at room temperature to obtain a cylinder with a diameter of 3 mm and a length of 6 mm;

[0061] ③ The product obtained in step ② was placed in a muffle furnace and calcined in a programmed temperature manner of 100°C for 30 min, 150°C for 30 min, 200°C for 30 min, 300°C for 60 min, 400°C for 60 min, 500°C for 60 min, 600°C for 120 min and 700°C for 180 min, and then naturally cooled to room temperature to obtain catalyst A.

[0062] Only the masses of strontium hydrogen phosphate, zirconium hydrogen phosphate, barium hydrogen phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate and aluminum sol in the preparation method of catalyst A were changed, and the other conditions were the same as those in catalyst example 1, and catalysts B, C, D, E, F, and G were prepared respectively. The specific parameters are shown in Table 1.

[0063] Table 1

[0064]

[0065] Device Example 1,

[0066] The fixed bed catalytic reactor used consists of a gasification chamber and a tubular reactor directly below the gasification chamber, the two are connected by a flange, the top and bottom of the tubular reactor are filled with ceramic rings, and the middle part is filled with a solid acid catalyst; the inner diameter (diameter) of the gasification chamber is 25 mm, and the tube length is 100 mm; the inner diameter of the middle part of the tubular reactor is 25 mm, and the tube length is 1000 mm, and the top and bottom of the middle part of the tubular reactor filled with ceramic rings are each 100 mm long.

[0067] The products obtained in the following cases were verified to be correct using conventional methods.

[0068] Embodiment 1:

[0069] 1) loading the solid acid catalyst E into the middle part of the tubular reactor;

[0070] 2) 150.5 g (1 mol) of raw material triethanolamine and 112.5 g (0.75 mol of urea) of 40% aqueous solution of urea were stirred at room temperature to obtain a raw material solution;

[0071] The raw material liquid is uniformly injected by using an injection pump, and the raw material liquid is vaporized in a 350°C vaporization chamber and then continuously aminated by a solid acid catalyst in a tubular reactor, the liquid weight hourly space velocity of the raw material liquid is 1 / h, the reaction pressure is 0.1Mpa, and the reaction temperature is 350°C;

[0072] In this case, the molar ratio of nitrogen atoms in triethanolamine and urea is 1:1.5;

[0073] 3) The reaction liquid obtained in step 2) is collected by condensing through a condenser, and is put into a distillation kettle for atmospheric distillation, and the fraction collected at a tower temperature of 10 to 130° C. is a light component, which is recycled; the fraction collected at a tower temperature of 130 to 175° C. is a TEDA fraction, and the remaining fraction in the distillation kettle is a heavy component, which is used to compound into a functional foaming catalyst.

[0074] TEDA (triethylenediamine) is subjected to secondary distillation (normal pressure distillation, collecting the fraction with a tower temperature of 130-175°C) to obtain a qualified TEDA product, that is, the water content of TEDA is less than 1%, and the GC content is greater than 99% after being dissolved in ethanol.

[0075] The light components are mainly morpholine and its derivatives (also including water); the heavy components are mainly morpholine ethanol and its derivatives. According to the structural characteristics of tertiary amine nitrogen atoms, the present invention uses them to compound into a functional foaming catalyst.

[0076] Note: As a conventional technique, the reaction liquid obtained in step 2) is collected by condensation using a condenser, and a sample is taken for gas phase analysis to detect the conversion rate of triethanolamine and to calculate the theoretical yield of each component.

[0077] In Examples 2 to 5, the amount of triethanolamine remains unchanged at 150.5 g, and the 40% urea aqueous solution is still selected, and the amount of the 40% urea aqueous solution is changed accordingly, thereby changing the molar ratio of triethanolamine to nitrogen atoms in urea in Example 1; the rest is the same as Example 1. The corresponding reaction conditions and corresponding results are shown in Table 2.

[0078] Example 6-Example 7 changes the weight hourly space velocity in Example 1, and the rest is the same as Example 1. The corresponding reaction conditions and corresponding results are shown in Table 2.

[0079] Examples 8 to 10 The reaction temperature in the tubular reactor in Example 1 was changed, and the rest was the same as Example 1. The corresponding reaction conditions and corresponding results are shown in Table 2.

[0080] Example 11-Example 12 The reaction pressure in the tubular reactor in Example 1 was changed, and the rest was the same as Example 1. The corresponding reaction conditions and corresponding results are shown in Table 2.

[0081] Table 2

[0082]

[0083]

[0084] Triethanolamine conversion rate = 1-chromatographic area percentage of triethanolamine in the product;

[0085] Morpholine yield = chromatographic peak area of ​​morpholine in the product / chromatographic peak area of ​​morpholine in the standard sample;

[0086] TEDA yield = chromatographic peak area of ​​TEDA in the product / chromatographic peak area of ​​TEDA in the standard sample;

[0087] Morpholineethanol yield = chromatographic peak area of ​​morpholineethanol in the product / chromatographic peak area of ​​morpholineethanol in the standard sample;

[0088] The calculation formulas for the above conversion rate and yield belong to conventional techniques.

[0089] Example 13: Light component is recycled once:

[0090] The "40% urea aqueous solution 112.5 g" in Example 1 is changed to "40% urea aqueous solution 90 g, 22.5 g of the light component obtained in Example 1", that is, the light component replaces 20% of the total amount of the urea aqueous solution; the rest is the same as Example 1.

[0091] Embodiment 14, light component is recycled twice:

[0092] Change “22.5 g of light component obtained in Example 1” to “22.5 g of light component obtained in Example 13”, and the rest is the same as Example 13.

[0093] By analogy, Example 15 is obtained, and the light component is recycled 3 times, that is, "22.5 g of light component obtained in Example 1" is changed to "22.5 g of light component obtained in Example 14", and the rest is the same as Example 13.

[0094] The reaction conditions and results corresponding to the above Examples 13 to 15 are shown in Table 3.

[0095] Table 3

[0096]

[0097] Examples 16 to 23: The solid acid catalyst E used in Example 1 was replaced with the catalyst described in Table 4 below, and the rest was the same as Example 1. The corresponding results are shown in Table 4.

[0098] Table 4

[0099]

[0100]

[0101] Examples 24 to 26: The "112.5 g of 40% urea aqueous solution" used in Example 1 was replaced with an aqueous solution of a nitrogen source as described in Table 5 below, that is, the molar ratio of triethanolamine to nitrogen atoms in the nitrogen source was maintained at 1:1.5, and the rest was the same as in Example 1. The corresponding reaction conditions and corresponding results are shown in Table 5.

[0102] Table 5

[0103]

[0104] Example 27. Preparation method of a functional foaming catalyst: Add 20 g of the heavy component in Example 1, 100 g of amine catalyst A33, 100 g of dipropylene glycol, and 20 g of PPG-2000 into a three-necked flask, heat to 60°C under nitrogen protection, continue stirring for 2 hours, cool to room temperature, add 80 g of bis(dimethylamino)ethyl ether, continue stirring at high speed at room temperature for 1 hour, and obtain a functional foaming catalyst A.

[0105] Example 28. Preparation method of a functional foaming catalyst: Add 30 g of the heavy component in Example 1, 90 g of amine catalyst A33, 100 g of dipropylene glycol and 30 g of PPG-2000 into a three-necked flask, heat to 60°C under nitrogen protection, stir continuously for 2 hours, cool to room temperature, add 80 g of bis(dimethylamino)ethyl ether, continue stirring at high speed at room temperature for 1 hour, and obtain a functional foaming catalyst B.

[0106] Example 29. Preparation method of a functional foaming catalyst: Add 40 g of the heavy component in Example 1, 100 g of amine catalyst A33, 100 g of dipropylene glycol, and 20 g of PPG-2000 into a three-necked flask, heat to 60°C under nitrogen protection, continue stirring for 2 hours, cool to room temperature, add 60 g of bis(dimethylamino)ethyl ether, continue stirring at high speed at room temperature for 1 hour, and obtain a functional foaming catalyst C.

[0107] Experiment 1: The functional foaming catalyst obtained in Example 27 was used to prepare a low-density polyurethane soft foam (polyurethane soft foam). The preparation process is as follows:

[0108] Add PPG-2000, monofluorodichloroethane, flame retardant TPP, water, silicone oil 815H, stannous octoate, and functional foaming catalyst A (Example 27) in Table 6 to a mixing barrel in sequence, mix and stir with a stirrer for 10 seconds, control the stirrer speed to 4000 rad / min, let stand for 2 minutes, then pour toluene diisocyanate (TDI-80) with a 2,4-body content of 80% into the mixing barrel, control the temperature between 25-32°C, start timing, stir quickly at 4000 rad / min for 3 seconds, pour the mixture into a foaming box for foaming, the reaction time is 51 seconds, and cut into the required size after ripening. The soft foam density is tested to be 6.9g / cm 3 .

[0109] Silicone oil 815H can be purchased from Nantong Hengguangda Polyurethane Materials Co., Ltd.

[0110] Experiment 2: The functional foaming catalyst A (Example 27) in Experiment 1 was replaced with the functional foaming catalyst B (Example 28), the dosage of the corresponding components in Experiment 1 was changed, and the standing time, rapid stirring time, and reaction time were changed accordingly. The rest was the same as Experiment 1. The details are shown in Table 6. The soft foam density was tested to be 10.2 g / cm 3 .

[0111] Experiment 3: The functional foaming catalyst A (Example 27) in Experiment 1 was replaced with the functional foaming catalyst C (Example 29), the dosage of the corresponding components in Experiment 1 was changed, and the standing time, rapid stirring time, and reaction time were changed accordingly. The rest was the same as Experiment 1. The details are shown in Table 6. The soft foam density was tested to be 8.5 g / cm 3 .

[0112] Table 6

[0113]

[0114]

[0115] Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and there are many variations. All variations that can be directly derived or associated with the content disclosed by a person skilled in the art should be considered as the protection scope of the present invention.

Claims

1. A method for producing triethylenediamine and a functional foaming catalyst from triethanolamine, characterized in that The following steps are involved: Step 1: using an aqueous solution of triethanolamine and a nitrogen source as a raw material liquid, reacting in a fixed bed reactor loaded with a solid acid catalyst, the pressure of the fixed bed reactor is 0.1-0.5 MPa, the temperature is 300-400° C., and the feed weight hourly space velocity of the raw material liquid is 0.2-2 / h; The molar ratio of nitrogen atoms in the nitrogen source to triethanolamine is 1-4.0:1; The product obtained by the reaction is distilled at normal pressure in a distillation kettle, and the fraction at 10-130°C is collected as a light component; the fraction at 130-175°C is collected as a triethylenediamine fraction, and the remaining in the distillation kettle is a heavy component, which is used for compounding into a functional foaming catalyst; The nitrogen source substance is a substance that can decompose ammonia, such as urea or ammonium carbonate; The preparation method of the solid acid catalyst is: The aluminum sol as a carrier and the active component are uniformly mixed to form a catalyst raw material; The catalyst raw material is first extruded at room temperature by a twin-screw extruder, then calcined by a programmed temperature rise method, and then naturally cooled to room temperature to obtain a solid acid catalyst; the programmed temperature rise is: calcination at 100±10°C for 30±5min, calcination at 150±10°C for 30±5min, calcination at 200±10°C for 30±5min, calcination at 300±10°C for 60±5min, calcination at 400±10°C for 60±5min, calcination at 500±10°C for 60±5min, calcination at 600±10°C for 120±5min, and calcination at 700±10°C for 180±5min; The active component is composed of the following ingredients in parts by weight: 60-90 parts of strontium hydrogen phosphate, 5-20 parts of zirconium hydrogen phosphate, 5-10 parts of barium hydrogen phosphate, 0-5 parts of calcium hydrogen phosphate, and 0-5 parts of magnesium hydrogen phosphate; The active component accounts for 80-95% of the total weight of the catalyst raw materials; the carrier accounts for 5-20% of the total weight of the catalyst raw materials.

2. The method for producing triethylenediamine and a functional foaming catalyst mainly from triethanolamine according to claim 1, characterized in that: The light component is recycled as a reaction raw material; when the light component is recovered and recycled, it is used in the form of replacing an aqueous solution of a nitrogen source substance having a weight fraction of 20±5%.

3. The method for producing triethylenediamine and a functional foaming catalyst mainly from triethanolamine according to claim 1 or 2, characterized in that It also includes the following step 2: Step 2: preparing a functional foaming catalyst by compounding the heavy components; The raw materials of the functional foaming catalyst are composed of the following components by weight: heavy component 5%~15%, amine catalyst A33 25%~35%, dipropylene glycol 25%~35%, PPG-2000 5%~15%, bis(dimethylamino)ethyl ether 20%~30%; The heavy component, amine catalyst A33, dipropylene glycol and PPG-2000 were added into a container, heated to 60±10°C under the protection of inert gas, stirred continuously for 2±0.5h, cooled to room temperature, and bis(dimethylamino)ethyl ether was added, and stirred at high speed for 1±0.5h at room temperature to obtain a functional foaming catalyst.

4. The method of producing triethylenediamine and a functional foaming catalyst mainly from triethanolamine according to claim 3, characterized in that The step 1 comprises the following steps: 1) Loading a solid acid catalyst into a fixed bed catalytic reactor; 2) Stirring the aqueous solution of triethanolamine and nitrogen source substance at room temperature to form raw material liquid, and then injecting the raw material liquid at a uniform speed by using an injection pump, the raw material liquid is vaporized in the vaporization chamber and then continuously aminated by the solid acid catalyst in the reactor, the feed weight hourly space velocity of the raw material liquid is 0.2~2 / h, the reaction pressure is 0~0.5MPa, and the temperature is 300~400℃; Weight hourly space velocity = feed weight of raw liquid per hour / loading weight of solid acid catalyst; 3) The reaction liquid obtained in step 2) is collected by condensing through a condenser, and subjected to atmospheric distillation in a distillation kettle. The fraction at 10-130° C. is collected as a light component; the fraction at 130° C.-175° C. is collected as a TEDA fraction, and the remaining fraction in the distillation kettle is a heavy component.

5. The method for producing triethylenediamine and a functional foaming catalyst mainly from triethanolamine according to claim 4, characterized in that: The aqueous solution of the nitrogen source substance is a saturated aqueous solution of the nitrogen source substance.

6. The method for producing triethylenediamine and a functional foaming catalyst mainly from triethanolamine according to claim 1, characterized in that: The active component is composed of the following ingredients by weight: 80 g strontium hydrogen phosphate, 10 g zirconium hydrogen phosphate, 5 g barium hydrogen phosphate, 3 g calcium hydrogen phosphate, and 2 g magnesium hydrogen phosphate; The aluminum sol is any of the following: 15 g, 10 g, 5 g.

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