A mor-containing molecular sieve composition for continuous synthesis of polyurethane using tertiary amine catalysts and its preparation method.

Abstract

The present invention relates to the technical field of molecular sieve catalysts, and in particular to a molecular sieve composition containing MOR for continuous synthesis of polyurethane using a tertiary amine catalyst and a preparation method thereof. The composition comprises the following raw materials in parts by weight: 30 to 35 parts of MOR molecular sieves, 20 to 30 parts of alumina binder, 15 to 20 parts of extrusion aids, and 2 to 4 parts of adhesives. The molecular sieve composition containing MOR prepared by the present invention, wherein the MOR molecular sieve is acidified and then a novel molecular sieve catalyst obtained by silane hybridization is used to reduce the use of morpholine and improve the utilization rate of morpholine. By adding the molecular sieve composition containing MOR prepared by the present invention, the consumption of expensive raw material morpholine is reduced, thereby reducing the production cost of the enterprise for synthesizing N-methylmorpholine.

Description

Technical Field

[0001] This invention relates to the field of molecular sieve catalyst technology, and in particular to a molecular sieve composition containing Mor for the continuous synthesis of tertiary amine catalysts for polyurethane and its preparation method. Background Technology

[0002] N-Methylmorpholine is an important organic chemical intermediate, a colorless to yellow liquid compound with an amine odor, with the chemical formula C5H11NO. Its CAS number is 109-02-4, and its molecular weight is 101.15. It possesses dual properties of tertiary amine and ether, and is widely used as a chemical intermediate, extractant, corrosion inhibitor, and surfactant. In the polyurethane industry, N-methylmorpholine is used as a catalyst for polyester-type polyurethane flexible foam.

[0003] There are many processes for synthesizing N-methylmorpholine. Based on the raw materials, there are the morpholine method, the N-methyldiethanol method, the diethanolamine method, the diethylene glycol method, and the dichloroethyl ether method. Among these, the methylation method using morpholine as a raw material has been the most studied and is also an important method for synthesizing N-methylmorpholine. However, the morpholine methylation method has high raw material morpholine prices and requires precious metal catalysts, resulting in high production costs. It also generates large amounts of formaldehyde-containing industrial wastewater, which is difficult to treat. Other methods generally use concentrated sulfuric acid for dehydration, resulting in high levels of waste and low yields.

[0004] Based on the above, this invention proposes a mor molecular sieve composition for the continuous synthesis of tertiary amine catalysts for polyurethane and its preparation method. Summary of the Invention

[0005] The purpose of this invention is to provide a mor molecular sieve composition for the continuous synthesis of polyurethane using tertiary amine catalysts and its preparation method.

[0006] To achieve the above objectives, the present invention provides a Mor molecular sieve composition for the continuous synthesis of polyurethane using tertiary amine catalysts, the composition comprising the following raw materials in parts by weight: 30-35 parts Mor molecular sieve, 20-30 parts alumina binder, 15-20 parts extrusion aid, and 2-4 parts adhesive.

[0007] Preferably, the alumina binder is one of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide, sodium aluminate, boehmite, and aluminum isopropoxide.

[0008] Preferably, the extrusion aid is selected from one or more of starch, guar gum, hydroxyethyl methylcellulose, methylcellulose, and polyethylene glycol.

[0009] Preferably, the adhesive is a nitric acid solution with a mass fraction of 3%.

[0010] Preferably, the Mor molecular sieve is processed by the following steps:

[0011] (1) Take Mor molecular sieve and organic weak acid solution, mix them evenly at a mass ratio of 1g (Mor molecular sieve): 20-25ml (organic weak acid solution), stir at 30-35℃ for 2-2.5h, then filter, wash with deionized water, and dry at 60-70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0012] (2) Take organic weak acid modified Mor molecular sieve and toluene, and mix them at a mass ratio of 1g (Mor molecular sieve): 50-60ml (toluene) to form a toluene suspension. Then take organosilane and add it to the toluene suspension at a mass ratio of 1g (Mor molecular sieve): 30-40ml (organosilane). Mix well and stir at 25-30℃ for 24h. Filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12h to obtain the product.

[0013] Preferably, the organic weak acid in step (1) is one of acetic acid, oxalic acid, benzoic acid, sorbic acid, citric acid, and malic acid.

[0014] Preferably, the concentration of the organic weak acid solution in step (2) is 7.0 to 8.0 mol / L.

[0015] Preferably, the organosilane is an organosilane containing a trimethoxy structure.

[0016] Preferably, the organosilane containing the trimethoxy structure has the general formula C1. X H Y O Z Si, where X≥5, Z≤5.

[0017] Preferably, the organosilane containing the trimethoxy structure is one of phenyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and vinyltrimethoxysilane.

[0018] Preferably, the organosilane containing the trimethoxy structure is phenyltrimethoxysilane.

[0019] This invention also provides a method for preparing a Mor-containing molecular sieve composition for the continuous synthesis of tertiary amine catalysts for polyurethane, the method comprising the following steps:

[0020] (1) Take Mor molecular sieve and organic weak acid solution, mix them evenly at a mass ratio of 1g (Mor molecular sieve): 20-25ml (organic weak acid solution), stir at 30-35℃ for 2-2.5h, then filter, wash with deionized water, and dry at 60-70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0021] (2) Take organic weak acid modified Mor molecular sieve and toluene, mix them at a mass ratio of 1g (Mor molecular sieve): 50-60ml (toluene) to form a toluene suspension, then take organosilane at a mass ratio of 1g (Mor molecular sieve): 30-40ml (organosilane) to the toluene suspension and mix them evenly. Stir at 25-30℃ for 24h, filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12h to obtain silane hybrid Mor molecular sieve.

[0022] (3) Mix the silane-hybridized Mor molecular sieve with alumina binder, extrusion aid and adhesive, roll it thoroughly and then extrude it into strips. Dry it at 100±5℃ for 10 to 12 hours, calcine it at 550 to 600℃ for 4.5 to 5.0 hours, and crush it into 20 to 30 mesh particles to obtain the product.

[0023] The present invention also provides the use of the aforementioned mor molecular sieve composition in the process of synthesizing tertiary amine catalysts for polyurethane.

[0024] The process of synthesizing polyurethane using a tertiary amine catalyst is the reaction of morpholine with methanol to produce N-methylmorpholine.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The MOR-containing molecular sieve composition prepared by this invention, wherein the MOR molecular sieve is acidified and then a novel molecular sieve catalyst obtained by silane hybridization is used, can reduce the use of morpholine and improve the utilization rate of morpholine. By adding the MOR-containing molecular sieve composition prepared by this invention, the production cost of synthesizing N-methylmorpholine can be reduced by reducing the consumption of expensive raw material morpholine.

[0027] 2. The raw materials for this invention are abundant and reasonably priced in China, which means that there are no high cost restrictions on its large-scale production. At the same time, the preparation method is simple and the overall production cost is not high, which is conducive to large-scale industrial production. Detailed Implementation

[0028] Example 1

[0029] Weigh the specific raw materials according to Table 1. The preparation steps are as follows:

[0030] (1) Take Mor molecular sieve and acetic acid solution, mix them evenly, stir at 30℃ for 2.5h, then filter, wash with deionized water, and dry at 60℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0031] (2) Take organic weak acid modified Mor molecular sieve and toluene, mix them to form a toluene suspension, then add organosilane to the toluene suspension and mix evenly. Stir at 25°C for 24 hours, filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12 hours to obtain silane hybrid Mor molecular sieve.

[0032] (3) Mix the silane-hybridized Mor molecular sieve with boehmite, guar gum powder and nitric acid solution (3%), knead thoroughly, extrude into strips, dry at 100±5℃ for 10h, calcine at 550℃ for 5.0h, and crush into 20-30 mesh particles to obtain the product.

[0033] Example 2

[0034] Weigh the specific raw materials according to Table 1. The preparation steps are as follows:

[0035] (1) Take Mor molecular sieve and acetic acid solution, mix them evenly, stir at 35℃ for 2 hours, then filter, wash with deionized water, and dry at 70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0036] (2) Take organic weak acid modified Mor molecular sieve and toluene, mix them to form a toluene suspension, then add organosilane to the toluene suspension and mix evenly. Stir at 30°C for 24 hours, filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12 hours to obtain silane hybrid Mor molecular sieve.

[0037] (3) Mix the silane-hybridized Mor molecular sieve with boehmite, guar gum powder and nitric acid solution (3%), knead thoroughly, extrude into strips, dry at 100±5℃ for 12h, calcine at 600℃ for 4.5h, and crush into 20-30 mesh particles to obtain the product.

[0038] Example 3

[0039] Weigh the specific raw materials according to Table 1. The preparation steps are as follows:

[0040] (1) Take Mor molecular sieve and acetic acid solution, mix them evenly, stir at 35℃ for 2.5h, then filter, wash with deionized water, and dry at 70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0041] (2) Take organic weak acid modified Mor molecular sieve and toluene, mix them to form a toluene suspension, then add organosilane to the toluene suspension and mix evenly. Stir at 30°C for 24 hours, filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12 hours to obtain silane hybrid Mor molecular sieve.

[0042] (3) Mix the silane-hybridized Mor molecular sieve with boehmite, guar gum powder and nitric acid solution (3%), knead thoroughly, extrude into strips, dry at 100±5℃ for 12h, calcine at 600℃ for 5.0h, and crush into 20-30 mesh particles to obtain the product.

[0043] Comparative Example 1

[0044] Weigh the specific raw materials according to Table 1. Unlike Example 3, the Mor molecular sieve was not subjected to silane hybridization treatment. The remaining preparation steps are as follows:

[0045] (1) Take Mor molecular sieve and acetic acid solution, mix them evenly, stir at 35℃ for 2.5h, then filter, wash with deionized water, and dry at 70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0046] (2) The organic weak acid modified Mor molecular sieve is mixed with boehmite, guar gum powder and nitric acid solution (3%), fully rolled and extruded into strips, dried at 100±5℃ for 12h, calcined at 600℃ for 5.0h, and crushed into 20-30 mesh particles to obtain the product.

[0047] Comparative Example 2

[0048] Weigh the specific raw materials according to Table 1. The difference from Example 3 is that the organosilane used is vinyltrimethoxysilane. The preparation steps are as follows:

[0049] (1) Take Mor molecular sieve and acetic acid solution, mix them evenly, stir at 35℃ for 2.5h, then filter, wash with deionized water, and dry at 70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0050] (2) Take organic weak acid modified Mor molecular sieve and toluene, mix them to form a toluene suspension, then add organosilane to the toluene suspension and mix evenly. Stir at 30°C for 24 hours, filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12 hours to obtain silane hybrid Mor molecular sieve.

[0051] (3) Mix the silane-hybridized Mor molecular sieve with boehmite, guar gum powder and nitric acid solution (3%), knead thoroughly, extrude into strips, dry at 100±5℃ for 12h, calcine at 600℃ for 5.0h, and crush into 20-30 mesh particles to obtain the product.

[0052] Comparative Example 3

[0053] Weigh the specific raw materials according to Table 1. The difference from Example 3 is that the organosilane used is 3-aminopropyltrimethoxysilane. The remaining preparation steps are as follows:

[0054] (1) Take Mor molecular sieve and acetic acid solution, mix them evenly, stir at 35℃ for 2.5h, then filter, wash with deionized water, and dry at 70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0055] (2) Take organic weak acid modified Mor molecular sieve and toluene, mix them to form a toluene suspension, then add organosilane to the toluene suspension and mix evenly. Stir at 30°C for 24 hours, filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12 hours to obtain silane hybrid Mor molecular sieve.

[0056] (3) Mix the silane-hybridized Mor molecular sieve with boehmite, guar gum powder and nitric acid solution (3%), knead thoroughly, extrude into strips, dry at 100±5℃ for 12h, calcine at 600℃ for 5.0h, and crush into 20-30 mesh particles to obtain the product.

[0057] Comparative Example 4

[0058] Weigh the specific raw materials according to Table 1. The difference from Example 3 is that the organosilane used is 3-glycidoxypropyltrimethoxysilane. The remaining preparation steps are as follows:

[0059] (1) Take Mor molecular sieve and acetic acid solution, mix them evenly, stir at 35℃ for 2.5h, then filter, wash with deionized water, and dry at 70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve.

[0060] (2) Take organic weak acid modified Mor molecular sieve and toluene, mix them to form a toluene suspension, then add organosilane to the toluene suspension and mix evenly. Stir at 30°C for 24 hours, filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12 hours to obtain silane hybrid Mor molecular sieve.

[0061] (3) Mix the silane-hybridized Mor molecular sieve with boehmite, guar gum powder and nitric acid solution (3%), knead thoroughly, extrude into strips, dry at 100±5℃ for 12h, calcine at 600℃ for 5.0h, and crush into 20-30 mesh particles to obtain the product.

[0062] Table 1

[0063]

[0064]

[0065] Example 4: Evaluation of the synthesis of N-methylmorpholine catalyzed by p-morpholine and methanol

[0066] Use 10m each of the prepared Examples 1-3 and Comparative Examples 1-4 3 The reactor, which is being installed in an industrial facility, is simultaneously loaded with 0.2m... 3 A metal catalyst (Cr 5%, Cu 22%, TiO 21%, Pt 0.5%, balance Ni) was used. The molar ratio of morpholine to methanol was 1:15 per hour. The catalyst was preheated, vaporized, and mixed with circulating hydrogen before entering the reactor. The reaction pressure was controlled at 0.6 MPa, the reaction temperature at 150℃, and the reaction time at 3 h. After the reaction, the crude N-methylmorpholine was cooled by heat exchange and then sent to a crude N-methylmorpholine storage tank. Samples were taken and analyzed by gas chromatography. The conversion efficiency results are shown in Table 2.

[0067] Take 10m each of Example 3 and Comparative Examples 3 and 4 3 The reactor, which is being installed in an industrial facility, is simultaneously loaded with 0.2m... 3 A metal catalyst (Cr 5%, Cu 22%, TiO 21%, Pt 0.5%, balance Ni) was used. The molar ratio of morpholine to methanol was 1:25 per hour. The catalyst was preheated, vaporized, and mixed with circulating hydrogen before entering the reactor. The reaction pressure was controlled at 0.6 MPa, the reaction temperature at 150℃, and the reaction time at 3 h. After the reaction, the crude N-methylmorpholine was cooled by heat exchange and then transferred to a crude N-methylmorpholine storage tank. Samples were taken and analyzed by gas chromatography. The conversion efficiency results are shown in Table 3.

[0068] Take 10m each of Example 3 and Comparative Example 4 3 The reactor, which is being installed in an industrial facility, is simultaneously loaded with 0.2m... 3 A metal catalyst (Cr 5%, Cu 22%, TiO 21%, Pt 0.5%, balance Ni) was used. The molar ratio of morpholine to methanol was 1:30 per hour. The catalyst was preheated, vaporized, and mixed with circulating hydrogen before entering the reactor. The reaction pressure was controlled at 0.6 MPa, the reaction temperature at 150℃, and the reaction time at 3 h. After the reaction, the crude N-methylmorpholine was cooled by heat exchange and then transferred to a crude N-methylmorpholine storage tank. Samples were taken and analyzed by gas chromatography. The conversion efficiency results are shown in Table 4.

[0069] Table 2

[0070]

[0071]

[0072] Table 3

[0073]

[0074] Table 4

[0075]

[0076] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. The use of a mor molecular sieve composition in the reaction of morpholine with methanol to produce N-methylmorpholine, characterized in that, The composition comprises the following raw materials in parts by weight: 30-35 parts of Mor molecular sieve, 20-30 parts of alumina binder, 15-20 parts of extrusion aid, and 2-4 parts of adhesive; The MOR molecular sieve is processed by the following steps: (1) Take Mor molecular sieve and organic weak acid solution, mix them evenly at a mass ratio of 1g Mor molecular sieve: 20~25ml organic weak acid solution, stir at 30~35℃ for 2~2.5h, then filter, wash with deionized water, and dry at 60~70℃ to constant weight to obtain organic weak acid modified Mor molecular sieve. (2) Take organic weak acid modified Mor molecular sieve and toluene, and mix them in a mass ratio of 1g Mor molecular sieve: 50~60ml toluene to form a toluene suspension. Then take organosilane and add it to the toluene suspension in a mass ratio of 1g Mor molecular sieve: 30~40ml organosilane. Mix evenly and stir at 25~30℃ for 24 h. Filter, wash the filter residue with anhydrous ethanol 3 times, centrifuge, and vacuum dry for 12 h to obtain silane hybrid Mor molecular sieve. The organosilane is phenyltrimethoxysilane.

2. The use according to claim 1, characterized in that, The organic weak acid in step (1) is one of acetic acid, oxalic acid, benzoic acid, sorbic acid, citric acid, and malic acid.

3. The use according to claim 1, characterized in that, The concentration of the organic weak acid solution in step (1) is 7.0~8.0 mol / L.

4. The use according to claim 1, characterized in that, The MOR-containing molecular sieve composition was prepared by the following method: The silane-hybridized Mor molecular sieve is mixed with alumina binder, extrusion aid, and adhesive, fully rolled, extruded into strips, dried at 100±5℃ for 10~12h, calcined at 550~600℃ for 4.5~5.0h, and crushed into 20~30 mesh particles to obtain the final product.

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