A process for drying alpha-olefins

Abstract

The application provides a method for drying alpha-olefins, comprising: contacting alpha-olefins containing trace water with a metal organic framework coordination polymer, so as to remove the trace water in the alpha-olefins. The application can achieve the purpose of deep water removal of alpha-olefins, and expand the types of water removal materials for alpha-olefins.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of raw material pretreatment, in particular to a method for drying alpha-olefins. BACKGROUND

[0002] Alpha-olefins (C5 and above liquid olefins) are an important organic raw material and intermediate product, which are widely used in co-monomer, poly-alpha-olefins, surfactants and other fine chemicals. Alpha-olefin preparation technologies include paraffin cracking, Fischer-Tropsch synthesis and ethylene oligomerization processes. The alpha-olefin raw materials prepared by these processes contain various impurities such as H2O, O2, CO2, CO, etc. With the society's desire for high-performance products, alpha-olefins are increasingly used to prepare high-performance polyolefins and poly-alpha-olefin lubricating oil base products. These high-performance product preparation technologies require high-quality alpha-olefins, which requires deep purification of alpha-olefins. Water is an important impurity affecting the quality of alpha-olefins, and unqualified water content directly affects the catalytic polymerization of alpha-olefins, causing economic losses.

[0003] Currently, the process technology method for removing water from alpha-olefins is mainly through adsorption by adsorbents. Molecular sieves are the most commonly used adsorbents for removing trace amounts of water using adsorption methods, such as 3A molecular sieves, 4A molecular sieves, 13X molecular sieves, etc. These molecular sieves have different pore sizes, generally between 0.3-1 nm, and a specific surface area generally less than 1000 m 2 / g. The surface of these molecular sieves has polarity and can interact with polar molecules through strong hydrogen bonding, dipole, electron transfer, etc., so it can remove trace amounts of water from alpha-olefins.

[0004] Metal organic framework coordination polymers (MOF) are a class of porous coordination polymers composed of organic compounds as ligands, metal ions as central ions, and coordination bonds as the action mode. This is a new type of porous material that has developed into a high-performance porous material in the past three decades. The pore size can reach 5 nm, and the specific surface area can reach 7500 m 2 / g. Compared with porous materials such as zeolites and carbon materials, porous coordination polymers have mild synthesis conditions, and based on the diversity of metal ion central coordination geometry and the modifiability of organic ligands, porous coordination polymers are easy to structure and modify. These structural characteristics are beneficial to the removal of trace amounts of water from alpha-olefins. SUMMARY

[0005] In view of the problems existing in the prior art, one of the purposes of the present application is to provide an application of metal organic framework coordination polymers in the field of trace water removal.

[0006] The second object of the present application is to provide a method for drying alpha-olefins.

[0007] The third object of the present application is to provide alpha-olefins with trace water removed corresponding to the above objects.

[0008] To achieve the above-mentioned one of the objects, the technical solutions adopted by the present application are as follows:

[0009] Application of a metal organic framework coordination polymer in the field of trace water removal in materials.

[0010] In some preferred embodiments of the present application, the application of the metal organic framework coordination polymer in the field of trace water removal in alpha-olefins with trace water.

[0011] The present inventors have found, through research, that metal organic framework coordination polymers (MOFs) have good adsorption effect on trace water, especially trace water in alpha-olefins, and can achieve the purpose of deep water removal of alpha-olefins. The present application can expand the types of alpha-olefin water removal materials.

[0012] According to the present application, the term "trace water" refers to the mass content of water in the material being less than 0.05%.

[0013] To achieve the above-mentioned second object, the technical solutions adopted by the present application are as follows:

[0014] A method for drying alpha-olefins, comprising: contacting alpha-olefins with trace water with a metal organic framework coordination polymer, thereby removing trace water in the alpha-olefins.

[0015] In some preferred embodiments of the present application, the conditions of the contacting include: the temperature of the contacting is 10℃-40℃.

[0016] In some preferred embodiments of the present application, the conditions of the contacting include: the temperature of the contacting is 20℃-35℃.

[0017] In some preferred embodiments of the present application, the conditions of the contacting include: the time of the contacting is 1h-72h, preferably 12h-48h.

[0018] According to the present application, the contacting mode is not limited as long as the alpha-olefins with trace water and the metal organic framework coordination polymer can be fully contacted. For example, the alpha-olefins with trace water and the metal organic framework coordination polymer can be placed in the same sealed container, and the alpha-olefins with trace water and the metal organic framework coordination polymer can be fully contacted by shaking or stirring.

[0019] In some preferred embodiments of the present application, the mass ratio of the metal-organic framework coordination polymer to the alpha-olefin is 1:(50-1000).

[0020] In some preferred embodiments of the present application, the mass ratio of the metal-organic framework coordination polymer to the alpha-olefin is 1:(100-500).

[0021] In some preferred embodiments of the present application, 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), 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).

[0022] According to the present application, the method for synthesizing the above-mentioned metal-organic framework coordination polymers is known in the art, and the specific synthesis steps can be referred to the existing literature or patents.

[0023] In some preferred embodiments of the present application, the alpha-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-icosene.

[0024] In some preferred embodiments of the present application, the alpha-olefin containing trace amount of water has a water content of greater than 0 ppm and less than or equal to 500 ppm, preferably 1 ppm-300 ppm, and more preferably 1 ppm-200 ppm.

[0025] To achieve the third aspect of the above-mentioned object, the present application adopts the following technical solutions:

[0026] An alpha-olefin product prepared according to the above method, wherein the water content of the alpha-olefin product is 0 ppm to 50 ppm, preferably 0 ppm to 30 ppm, more preferably 0 ppm to 20 ppm, further preferably 0 ppm to 10 ppm, and more further preferably 0 ppm to 5 ppm.

[0027] In some preferred embodiments of the present application, the water content of the alpha-olefin product is 0 ppm to 1 ppm.

[0028] According to the present application, the water content of the alpha-olefin product reaches the polymerization grade, and can meet the polymerization conditions of a polymerization catalyst with extremely high water content requirement.

[0029] The present application has at least the following advantages:

[0030] Firstly, the present application provides a new material suitable for alpha-olefin dehydration, which broadens the types of alpha-olefin dehydration materials.

[0031] Secondly, the method for drying alpha-olefin provided by the present application can deeply remove trace water in alpha-olefin, and the water content of alpha-olefin treated by the method of the present application can be reduced to below 5 ppm. DETAILED DESCRIPTION

[0032] The present application is described in detail below through examples, but the scope of protection of the present application is not limited to the following description.

[0033] The specific conditions not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be obtained through market channels.

[0034] Preparation Example 1

[0035] Preparation of metal-organic framework coordination polymer UiO-66:

[0036] 5 mmol of zirconium chloride, 5 mmol of terephthalic acid, 1 mL of 37 wt% concentrated hydrochloric acid, and 50 mL of N,N-dimethylformamide were added to a 100 mL autoclave, ultrasonicated for 15 minutes, sealed, heated at 120℃ for 2 days, naturally cooled, and filtered. Then, washed with N,N-dimethylformamide for 3 times, then soaked with methanol for 2 days, during which fresh methanol was replaced for soaking, then vacuum dried, followed by drying and activation at 150℃ in vacuum for 12 hours, to obtain a solid sample.

[0037] Preparation Example 2

[0038] Preparation of metal-organic framework coordination polymer UiO-66-NH2:

[0039] UiO-66-NH2was prepared following the procedure of Preparation Example 1, except that terephthalic acid was exchanged for 2-aminoterephthalic acid.

[0040] Preparation Example 3

[0041] Preparation of metal organic framework coordination polymer MIL-100(Al):

[0042] Into a 100 mL autoclave was added 7.5 mmol aluminum nitrate, 5 mmol of 1,3,5-benzenetricarboxylic acid, and 50 mL of ethanol, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, allowed to cool naturally, filtered. Then, rinsed 3 times with ethanol, then soaked in ethanol for 2 days, changing the fresh ethanol soak, then vacuum dried, followed by drying activation at 150 °C in vacuum for 12 hours to obtain a solid sample.

[0043] Preparation Example 4

[0044] Preparation of metal organic framework coordination polymer Zn-MOF-508:

[0045] Into a 100 mL autoclave was added 5 mmol zinc nitrate, 5 mmol of terephthalic acid, 2.5 mmol of 4,4'-bipyridine, and 25 mL of ethanol and 25 ml of N,N- dimethylformamide, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, allowed to cool naturally, filtered. Then, rinsed 3 times with N,N-dimethylformamide, then soaked in methanol for 2 days, changing the fresh methanol soak, then vacuum dried, followed by drying activation at 150 °C in vacuum for 12 hours to obtain a solid sample.

[0046] Preparation Example 5

[0047] Preparation of metal organic framework coordination polymer CAU-10-H:

[0048] Into a 100 mL autoclave was added 5 mmol aluminum sulfate, 5.2 mmol of isophthalic acid, and 40 mL of water and 10 ml of N,N-dimethylformamide, sonicated for 15 minutes, sealed, heated at 120 °C for 2 days, allowed to cool naturally, filtered. Then, rinsed 3 times with N,N-dimethylformamide, then soaked in methanol for 2 days, changing the fresh methanol soak, then vacuum dried, followed by drying activation at 150 °C in vacuum for 12 hours to obtain a solid sample.

[0049] Preparation Example 6

[0050] Preparation of metal organic framework coordination polymer DUT-51(Zr):

[0051] Into a 100 mL autoclave, 5 mmol of zirconium chloride, 3.35 mmol of dithiophene [3,2-B:2',3'-D]thiophene-2,6-dicarboxylic acid, and 10 g of benzoic acid and 50 mL of N,N-dimethylformamide were added, ultrasonic for 15 minutes, sealed, heated at 120 °C for 2 days, naturally cooled, filtered. Then, washed with N,N-dimethylformamide for 3 times, then soaked with methanol for 2 days, during which fresh methanol was needed to soak, then vacuum dried, followed by drying in vacuum at 150 °C for 12 hours, to obtain a solid sample.

[0052] Example 1

[0053] Take 5 dry and clean sealed bottles, numbered a, b, c, d, e respectively. Use an electronic balance to weigh 1 g of activated UiO-66 prepared in Preparation Example 1 in five portions, respectively, and place them in the sealed bottles numbered a, b, c, d, e. Then weigh 200 g of sample 1-octene with different water contents into the sealed bottles numbered a, b, c, d, e, respectively. Then seal the sealed bottles a, b, c, d, e and store them in a glove box. Shake the sealed bottles every 2 hours, and after 1 day of storage, use a trace moisture analyzer to measure, and the results are shown in Table 1.

[0054] Table 1

[0055]

[0056] Example 2

[0057] Example 2 is set to be substantially the same as Example 1, except that UiO-66-NH2 prepared in Preparation Example 2 is used to replace UiO-66 in Example 1, and the test results are shown in Table 2.

[0058] Table 2

[0059]

[0060] Example 3

[0061] Example 3 is set to be substantially the same as Example 1, except that MIL-100(Al) prepared in Preparation Example 3 is used to replace UiO-66 in Example 1, and the test results are shown in Table 3.

[0062] Table 3

[0063]

[0064] Example 4

[0065] Example 4 was set up essentially the same as Example 1, except that Zn-MOF-508 prepared in Preparation Example 4 was used to replace UiO-66 in Example 1, and the test results are shown in Table 4.

[0066] Table 4

[0067]

[0068] Example 5

[0069] Example 5 was set up essentially the same as Example 1, except that CAU-10-H prepared in Preparation Example 5 was used to replace UiO-66 in Example 1, and the test results are shown in Table 5.

[0070] Table 5

[0071]

[0072] Example 6

[0073] Example 6 was set up essentially the same as Example 1, except that DUT-51(Zr) prepared in Preparation Example 6 was used to replace UiO-66 in Example 1, and the test results are shown in Table 6.

[0074] Table 6

[0075]

[0076] It should be noted that the above-described examples are only used to explain the present application, and do not constitute any limitation on the present application. The present application is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified as specified within the scope of the claims of the present application, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications having the same function.

Claims

1. Use of a metal organic framework coordination polymer in the field of trace water removal in an alpha-olefin containing trace water; 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), 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); a mass ratio of the metal organic framework coordination polymer to the alpha-olefin is 1:(50-1000); the alpha-olefin containing trace water has a water content of greater than 0 ppm and less than or equal to 500 ppm.

2. A method of drying alpha-olefins comprising: contacting an alpha-olefin containing trace water with a metal organic framework coordination polymer, thereby removing the trace water in the alpha-olefin; 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), 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); a mass ratio of the metal organic framework coordination polymer to the alpha-olefin is 1:(50-1000); the alpha-olefin containing trace water has a water content of greater than 0 ppm and less than or equal to 500 ppm.

3. The method of claim 2, wherein, the contacting is performed at a temperature of 10-40°C for 1-72 hours.

4. The method of claim 3, wherein, the contacting is performed for 12-48 hours.

5. The method according to any one of claims 2-4, characterized in that, The mass ratio of the metal organic framework coordination polymer to the alpha-olefin is 1:(100-500).

6. The method according to any one of claims 2-4, characterized in that, The alpha-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-icosene.

7. The method according to any one of claims 2-4, characterized in that, In the alpha-olefin containing trace water, the water content is 1-300 ppm.

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

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