A combined reagent, apparatus and method for removing trace water from alpha-olefins

Abstract

The application provides a combined reagent, a device and a method for removing trace water in alpha-olefins. The device comprises a first dehydration unit filled with molecular sieves; a second dehydration unit filled with metal organic framework coordination polymers connected to, preferably in contact with, the first dehydration unit; wherein the device is provided with a feed pipe line in communication with the first dehydration unit; and / or the device is provided with a discharge pipe line in communication with the second dehydration unit. The first dehydration unit filled with molecular sieves and the second dehydration unit filled with metal organic framework coordination polymers can effectively remove trace water in alpha-olefins in cooperation.

Description

Technical Field

[0001] This invention relates to the field of dehydration technology for α-olefins, and specifically to a combination reagent, apparatus, and method for removing trace water from α-olefins. Background Technology

[0002] The double bond groups in alkenes have good reactivity and can undergo addition reactions such as hydrogenation, halogenation, hydration, hydrogen halide, hypohalogenation, sulfation, epoxidation, and polymerization. They can also be oxidized to break the double bond and generate aldehydes, carboxylic acids, etc.

[0003] Olefins are also major chemical raw materials in industrial production. Currently, widely used bulk olefin chemical raw materials include ethylene, propylene, 1-butene, 2-butene, and isobutene. Due to differences in production processes, most olefin products contain some oxygen-containing compounds, mainly water, ethers, alcohols, ketones, and aldehydes. Although their physical properties differ significantly from those of olefins, they are difficult to separate from olefins. Industrial processes generally use a combination of distillation and washing distillation, which is energy-intensive. For example, the production of isobutene from MTBE cracking contains oxygen-containing impurities such as methanol, dimethyl ether, and water; the production of isobutene from PO by-product TBA cracking contains impurities such as methanol, acetone, methyl tert-butyl ether, methyl ethyl ketone, isobutyraldehyde, tert-butanol, and water; and the production of ethylene and propylene from methanol contains impurities such as methanol, dimethyl ether, and propionaldehyde. Generally, solvent absorption and refining processes can only remove most of the oxygen-containing impurities. The presence of trace oxygen-containing impurities often affects the high-end applications of olefin monomers downstream, requiring more advanced purification processes to obtain high-purity olefin monomers.

[0004] With the growing demand for high-performance products, α-olefins are increasingly used to prepare high-performance polyolefins and polyα-olefin lubricating oil bases. The preparation technologies for these high-performance products require high-quality α-olefins, necessitating thorough purification. Water is a significant impurity affecting the quality of α-olefins; substandard water content directly impacts the catalytic polymerization of α-olefins, leading to economic losses. Summary of the Invention

[0005] In view of the problems existing in the prior art, one of the objectives of the present invention is to provide a combined reagent for removing trace water from α-olefins, which can effectively remove trace water from α-olefins through the synergistic cooperation of molecular sieves and metal-organic framework coordination polymers.

[0006] The second objective of this invention is to provide an application corresponding to the first objective.

[0007] The third objective of this invention is to provide an apparatus for removing trace water from α-olefins, which can effectively remove trace water from α-olefins by using a first dehydration unit filled with molecular sieves and a second dehydration unit filled with metal-organic framework coordination polymers in synergy.

[0008] The fourth objective of this invention is to provide an application corresponding to the third objective.

[0009] The fifth objective of this invention is to provide a method for removing trace amounts of water from α-olefins, corresponding to the above-mentioned objective.

[0010] To achieve one of the above objectives, the technical solution adopted by the present invention is as follows:

[0011] A combined reagent for removing trace amounts of water from α-olefins comprises: a molecular sieve and a metal-organic framework coordination polymer disposed downstream of the molecular sieve.

[0012] The inventors of this application discovered in their research that the surface of molecular sieves is polar, and it interacts strongly with polar molecules through hydrogen bonds, dipoles, electron transfer, and other interactions, thus enabling the extraction of trace amounts of water from α-olefins. Metal-organic framework (MOF) coordination polymers are a class of porous coordination polymers composed of organic compounds as ligands, metal ions as central ions, and coordination bonds as the interaction mechanism. This is a novel type of porous material, a high-performance porous material developed only in the last thirty years. Pore diameters can reach 5 nm, and specific surface areas can reach 7500 m². 2 / g. Compared to porous materials such as zeolites and carbon materials, porous coordination polymers offer milder synthesis conditions. Furthermore, due to the diversity of coordination geometries at the metal ion centers and the modifiability of organic ligands, porous coordination polymers are easily structurally controlled or modified. Metal-organic framework coordination polymers can achieve deep dehydration of α-olefins.

[0013] Traditional molecular sieves have advantages over MOFs in both synthesis methods and cost. MOFs, on the other hand, surpass traditional molecular sieves in pore size, specific surface area, and pore flexibility. These advantages allow MOFs to remove trace amounts of water from α-olefins at a greater depth than traditional molecular sieves. Combining the advantages of both adsorbents, a combined approach of traditional molecular sieves and MOFs can be used for the deep removal of trace amounts of water from α-olefins.

[0014] In some preferred embodiments of the present invention, the molecular sieve is in contact with the metal-organic framework coordination polymer.

[0015] In some preferred embodiments of the present invention, the molecular sieve and the metal-organic framework coordination polymer are in surface-to-surface contact.

[0016] According to the present invention, the surface-to-surface contact means that the molecular sieve and the metal-organic framework coordination polymer exist in the form of the molecular sieve layer and the metal-organic framework coordination polymer, respectively, and the two layers are in contact.

[0017] In some preferred embodiments of the present invention, the molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve.

[0018] In some preferred embodiments of the present invention, the metal-organic framework coordination polymer is selected from UiO-66, UiO-66-NH2, UiO-66-MM, UiO-66-Br, UiO-66-Br2, UiO-66-CO2H, UiO-67, MIL-100(Al), MIL-100(Fe), MIL-53(Al), MIL-53(Cr), MIL-127, MIL-101-NH2(Cr), and MIL-125-NH2(Ti). One or more of the following: Zn-MOF-508, Zn-DMOF-A, Zn-DMOF-TM, CAU-10-H, CAU-10-CH3, CAU-10-NO2, CAU-10-NH2, CAU-10-OH, CAU-10-OCH3, MOF-801-P, MOF-801-SC, MOF-802, MOF-804, MOF-841, DUT-51(Zr), DUT-51(Hf), and DUT-67(Zr).

[0019] In some preferred embodiments of the present invention, the mass ratio of the molecular sieve to the metal-organic framework coordination polymer is (1-1000):1, preferably (1-100):1, more preferably (1-50):1, further preferably (1-30):1, and even more preferably (5-20):1.

[0020] To achieve the second objective mentioned above, the technical solution adopted by the present invention is as follows:

[0021] Application of the combined reagent described in any of the above embodiments in the field of processing materials containing trace amounts of water, especially in the field of processing α-olefin materials containing trace amounts of water.

[0022] To achieve the third objective mentioned above, the technical solution adopted by the present invention is as follows:

[0023] An apparatus for removing trace amounts of water from α-olefins, comprising:

[0024] The first dewatering unit is filled with molecular sieves;

[0025] A second dehydration unit, filled with a metal-organic framework coordination polymer, is connected to the first dehydration unit;

[0026] The device is provided with a feed pipe that is connected to the first dewatering unit; and / or the device is provided with a discharge pipe that is connected to the second dewatering unit.

[0027] In some preferred embodiments of the present invention, the second dehydration unit is in contact with the first dehydration unit.

[0028] In some preferred embodiments of the present invention, the device is provided with a feed pipe that is connected to the first dehydration unit.

[0029] In some specific embodiments of the present invention, the feed pipeline can be either a feed inlet or a feed pipe.

[0030] In some preferred embodiments of the present invention, the device is provided with a discharge pipe, which is connected to the second dewatering unit.

[0031] In some specific embodiments of the present invention, the discharge pipeline can be either a discharge port or a discharge pipe.

[0032] In some specific embodiments of the present invention, the first dewatering unit and the second dewatering unit may be arranged in a fixed bed, with the first dewatering unit located on the lower layer of the fixed bed and the second dewatering unit located on the upper layer of the fixed bed. The feed inlet is located at the bottom of the fixed bed, and the discharge outlet is located at the top of the fixed bed.

[0033] In some preferred embodiments of the present invention, the molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve.

[0034] According to the present invention, the specific model of the molecular sieve is not particularly limited, as long as the model meets the requirements of the present invention.

[0035] In some preferred embodiments of the present invention, the metal-organic framework coordination polymer is selected from UiO-66, UiO-66-NH2, UiO-66-MM, UiO-66-Br, UiO-66-Br2, UiO-66-CO2H, UiO-67, MIL-100(Al), MIL-100(Fe), MIL-53(Al), MIL-53(Cr), MIL-127, MIL-101-NH2(Cr), and MIL-125-NH2(Ti). One or more of the following: Zn-MOF-508, Zn-DMOF-A, Zn-DMOF-TM, CAU-10-H, CAU-10-CH3, CAU-10-NO2, CAU-10-NH2, CAU-10-OH, CAU-10-OCH3, MOF-801-P, MOF-801-SC, MOF-802, MOF-804, MOF-841, DUT-51(Zr), DUT-51(Hf), and DUT-67(Zr).

[0036] In some preferred embodiments of the present invention, the mass ratio of the molecular sieve to the metal-organic framework coordination polymer is (1-1000):1.

[0037] In some preferred embodiments of the present invention, the mass ratio of the molecular sieve to the metal-organic framework coordination polymer is (1-100):1.

[0038] In some preferred embodiments of the present invention, the mass ratio of the molecular sieve to the metal-organic framework coordination polymer is (1-50):1.

[0039] In some preferred embodiments of the present invention, the mass ratio of the molecular sieve to the metal-organic framework coordination polymer is (1-30):1.

[0040] In some preferred embodiments of the present invention, the mass ratio of the molecular sieve to the metal-organic framework coordination polymer is (5-20):1.

[0041] According to the present invention, when the mass ratio of the molecular sieve to the metal-organic framework coordination polymer is within the above-mentioned range, the optimal removal effect of trace water can be obtained at a lower cost.

[0042] To achieve the fourth objective mentioned above, the technical solution adopted by the present invention is as follows:

[0043] Application of the above-mentioned device in the field of processing materials containing trace amounts of water.

[0044] In some preferred embodiments of the present invention, the above-described apparatus is used in the field of processing α-olefin materials containing trace amounts of water.

[0045] To achieve the fifth objective mentioned above, the technical solution adopted by the present invention is as follows:

[0046] A method for removing trace water from α-olefins includes: passing an α-olefin material containing trace water into the aforementioned apparatus, thereby causing the α-olefin material containing trace water to sequentially contact the molecular sieve and the metal-organic framework coordination polymer to obtain an α-olefin product.

[0047] In some preferred embodiments of the present invention, the contact conditions include a temperature of 10°C to 40°C.

[0048] In some preferred embodiments of the present invention, the α-olefin material containing trace amounts of water is present in the device for 10 min to 120 min.

[0049] According to the present invention, the flow rate of the α-olefin material containing trace amounts of water is not particularly limited, and in practical applications, those skilled in the art can adjust it according to the actual removal situation.

[0050] In some preferred embodiments of the present invention, the α-olefin is selected from one or more of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecanene, 1-hexadecene, 1-heptadecene, 1-heptadecene, 1-octadecene, 1-nonadecanene, and 1-eicosene.

[0051] In some preferred embodiments of the present invention, the water content in the α-olefin material containing trace amounts of water is 0 ppm to 500 ppm.

[0052] In some preferred embodiments of the present invention, the water content in the α-olefin material containing trace amounts of water is above 0 ppm and below 500 ppm.

[0053] In some preferred embodiments of the present invention, the water content in the α-olefin material containing trace amounts of water is 1 ppm to 300 ppm.

[0054] In some preferred embodiments of the present invention, the water content in the α-olefin material containing trace amounts of water is 1 ppm to 200 ppm.

[0055] In some preferred embodiments of the present invention, the water content in the α-olefin product is 0 ppm to 10 ppm.

[0056] In some preferred embodiments of the present invention, the water content in the α-olefin product is 0 ppm to 5 ppm.

[0057] According to the present invention, the term "trace water" refers to water with a mass content of less than 0.05%.

[0058] The beneficial effects of this invention lie at least in that it comprehensively utilizes the advantages of molecular sieves and MOFs, enabling the deep removal of trace water from α-olefins. The trace water content in α-olefins treated by the apparatus or method of this invention can be reduced to below 5 ppm. Attached Figure Description

[0059] Figure 1 This is a schematic diagram of the device used in Embodiment 1 of the present invention.

[0060] Figure 1 In the diagram, circles represent molecular sieves, squares represent metal-organic framework coordination polymers, horizontal lines between circles and squares represent the contact surfaces between the molecular sieves and metal-organic framework coordination polymers, vertical lines at the bottom represent the feed pipes, and vertical lines at the top represent the discharge pipes. Detailed Implementation

[0061] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited to the following description.

[0062] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0063] Unless otherwise specified, in the following embodiments:

[0064] 4A molecular sieves are obtained commercially. Before use, the 4A molecular sieves should be placed in a crucible, placed in a muffle furnace, and dried at 300°C for 8 hours.

[0065] 10X molecular sieves were obtained commercially. Before use, the 10X molecular sieves should be placed in a crucible, placed in a muffle furnace, and dried at 300°C for 8 hours.

[0066] Preparation Example 1

[0067] Preparation of the metal-organic framework coordination polymer UiO-66-NH2: 5 mmol zirconium chloride, 5 mmol 2-aminoterephthalic acid, 1 mL 37 wt% concentrated hydrochloric acid, and 50 mL N,N-dimethylformamide were added to a 100 mL autoclave. The mixture was sonicated for 15 minutes, sealed, and heated at 120 °C for 2 days. After natural cooling, the mixture was filtered. Then, it was washed three times with N,N-dimethylformamide, and then soaked in methanol for 2 days, replacing the methanol with fresh methanol each time. After vacuum drying, it was activated by drying at 150 °C under vacuum for 12 hours to obtain a solid sample.

[0068] Preparation Example 2

[0069] Preparation of metal-organic framework coordination polymer MIL-100(Al):

[0070] 7.5 mmol aluminum nitrate, 5 mmol trimesic acid, and 50 mL ethanol were added to a 100 mL autoclave, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, allowed to cool naturally, and filtered. The sample was then rinsed three times with ethanol, followed by soaking in ethanol for 2 days, replacing the ethanol with fresh ethanol each time. Afterward, it was vacuum dried, and then activated by drying at 150 °C under vacuum for 12 hours to obtain a solid sample.

[0071] Preparation Example 3

[0072] Preparation of metal-organic framework coordination polymer Zn-MOF-508:

[0073] 5 mmol zinc nitrate, 5 mmol terephthalic acid, 2.5 mmol 4,4'-bipyridine, 25 mL ethanol, and 25 mL N,N-dimethylformamide were added to a 100 mL autoclave. The autoclave was sonicated for 15 minutes, sealed, and heated at 120 °C for 2 days. After natural cooling, the mixture was filtered. Then, the sample was washed three times with N,N-dimethylformamide, and then soaked in methanol for 2 days, changing the methanol each time. After soaking, the sample was vacuum dried, and then activated by drying at 150 °C under vacuum for 12 hours to obtain a solid sample.

[0074] Preparation Example 4

[0075] Preparation of metal-organic framework coordination polymer CAU-10-H:

[0076] 5 mmol of aluminum sulfate, 5.2 mmol of isophthalic acid, 40 mL of water, and 10 mL of N,N-dimethylformamide were added to a 100 mL autoclave. The autoclave was sonicated for 15 minutes, sealed, and heated at 120 °C for 2 days. After natural cooling, the mixture was filtered. Then, the sample was washed three times with N,N-dimethylformamide and soaked in methanol for 2 days, changing the methanol each time. The sample was then vacuum dried and activated at 150 °C under vacuum for 12 hours to obtain a solid sample.

[0077] Preparation Example 5

[0078] Preparation of metal-organic framework coordination polymer DUT-51(Zr):

[0079] 5 mmol of zirconium chloride, 3.35 mmol of dithiophene[3,2-B:2',3'-D]thiophene-2,6-dicarboxylic acid, 10 g of benzoic acid, and 50 mL of N,N-dimethylformamide were added to a 100 mL autoclave. The autoclave was sonicated for 15 minutes, sealed, and heated at 120 °C for 2 days. After natural cooling, the mixture was filtered. Then, the sample was washed three times with N,N-dimethylformamide and soaked in methanol for 2 days, changing the methanol each time. The sample was then vacuum dried and activated at 150 °C under vacuum for 12 hours to obtain a solid sample.

[0080] Example 1

[0081] 100g of 4A molecular sieve was packed into the lower layer of the fixed bed, and 10g of UiO-66-NH2 prepared in Preparation Example 1 was packed into the lower layer of the fixed bed (e.g., Figure 1 (As shown in Table 1). 1-Octenene was conveyed by constant current from bottom to top, and samples were taken from the upper layer of the fixed bed. Moisture content was determined using a trace moisture analyzer, and the results are shown in Table 1.

[0082] Example 2

[0083] 100g of 4A molecular sieve was packed into the lower layer of the fixed bed, and 10g of MIL-100(Al) prepared in Preparation Example 2 was packed into the lower layer of the fixed bed (e.g., Figure 1 (As shown in Table 1). 1-Octenene was conveyed by constant current from bottom to top, and samples were taken from the upper layer of the fixed bed. Moisture content was determined using a trace moisture analyzer, and the results are shown in Table 1.

[0084] Example 3

[0085] 100g of 4A molecular sieve was packed into the lower layer of the fixed bed, and 10g of Zn-MOF-508 prepared in Preparation Example 3 was packed into the lower layer of the fixed bed (e.g., Figure 1 (As shown in Table 1). 1-Octenene was conveyed by constant current from bottom to top, and samples were taken from the upper layer of the fixed bed. Moisture content was determined using a trace moisture analyzer, and the results are shown in Table 1.

[0086] Example 4

[0087] 100g of 4A molecular sieve was packed into the lower layer of the fixed bed, and 10g of CAU-10-H prepared in Preparation Example 4 was packed into the lower layer of the fixed bed (e.g., Figure 1 (As shown in Table 1). 1-Octenene was conveyed by constant current from bottom to top, and samples were taken from the upper layer of the fixed bed. Moisture content was determined using a trace moisture analyzer.

[0088] Example 5

[0089] 100g of 4A molecular sieve was packed into the lower layer of the fixed bed, and 10g of DUT-51(Zr) prepared in Preparation Example 5 was packed into the lower layer of the fixed bed (e.g., Figure 1 (As shown in Table 1). 1-Octenene was conveyed by constant current from bottom to top, and samples were taken from the upper layer of the fixed bed. Moisture content was determined using a trace moisture analyzer.

[0090] Comparative Example 1

[0091] 110g of 4A molecular sieve was packed into the lower layer of a fixed bed. 1-Octenene was conveyed by constant current from bottom to top, and samples were taken from the upper layer of the fixed bed. Moisture content was determined using a trace moisture analyzer, and the results are shown in Table 1.

[0092] Comparative Example 2

[0093] 100g of 4A molecular sieve and 10g of 10X molecular sieve were added to the lower layer of the fixed bed (e.g., ...). Figure 1 (As shown in Table 1). 1-Octenene was conveyed by constant current from bottom to top, and samples were taken from the upper layer of the fixed bed. Moisture content was determined using a trace moisture analyzer.

[0094] Table 1

[0095]

[0096]

[0097] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for removing trace amounts of water from an alpha-olefin comprising: The α-olefin material containing trace water is introduced into a device for removing trace water in the α-olefin, so that the α-olefin material containing trace water is sequentially contacted with a molecular sieve and a metal organic framework coordination polymer, to obtain an α-olefin product, and the conditions of the contacting include: the temperature is 10-40℃; and the time for the α-olefin material containing trace water to stay in the device is 10-120 min, The device comprises: a first dehydration unit filled with a molecular sieve; a second dehydration unit filled with a metal organic framework coordination polymer, which is in contact with the first dehydration unit; wherein the device is provided with a feed pipe which is in communication with the first dehydration unit; and the device is provided with a discharge pipe which is in communication with the second dehydration unit; the molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 10X molecular sieve and 13X molecular sieve; and the metal organic framework coordination polymer is selected from one or more of UiO-66, UiO-66-NH2, UiO-66-MM, UiO-66-Br, UiO-66-Br2, UiO-66-CO2H, UiO-67, MIL-100(Al), MIL-100(Fe), MIL-53(Al), MIL-53(Cr), MIL-127, MIL-101-NH2(Cr), MIL-125-NH2(Ti), DUT-51(Zr), DUT-51(Hf) and DUT-67(Zr); the α-olefin is selected from one or more of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene; the water content in the α-olefin material containing trace water is 0-500 ppm; the water content in the α-olefin product is 0-10 ppm.

2. The method of claim 1, wherein, The mass ratio of the molecular sieve to the metal organic framework coordination polymer is (1-1000):

1.

3. The method of claim 2, wherein, The mass ratio of the molecular sieve to the metal organic framework coordination polymer is (1-100):

1.

4. The method of claim 2, wherein, The mass ratio of the molecular sieve to the metal organic framework coordination polymer is (5-20):

1.

5. The method of claim 2, wherein, The mass ratio of the molecular sieve to the metal organic framework coordination polymer is (10-50):

1.

6. The method of claim 2, wherein, The mass ratio of the molecular sieve to the metal organic framework coordination polymer is (20-30):

1.

7. The method according to any one of claims 1 to 6, characterized in that, The water content in the α-olefin material containing trace water is 1-300 ppm; and / or, the water content in the α-olefin product is 0-5 ppm.

8. The method of claim 7, wherein, The water content in the α-olefin material containing trace water is 1-200 ppm.

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