Adsorbent for efficiently separating 1-nonene and 2-methyl-1-octene and preparation method thereof

Abstract

The application relates to the technical field of adsorbents, and particularly discloses an adsorbent for efficiently separating 1-nonene and 2-methyl-1-octene and a preparation method thereof. The method specifically comprises the following steps: S1: preparing an aqueous solution of 0.5-3 mass parts of a transition metal salt, and impregnating 10 mass parts of a porous carrier; the transition metal salt is at least one selected from FeCl3, CuCl2 and CoCl2; the porous carrier is at least one selected from gamma-Al2O3, ZIF-8 and ZIF-20; and S2: performing solvent removal treatment on the impregnated porous carrier under an inert gas atmosphere to obtain the adsorbent. The adsorbent is mainly composed of the porous carrier and an active metal component. Compared with the porous carrier without the loaded transition metal salt, the adsorbent can improve the purity of 1-nonene. The method has a simple process flow, low raw material price and large-scale preparation potential.

Description

Technical Field

[0001] This invention relates to the field of adsorbent technology, specifically disclosing an adsorbent for the efficient separation of 1-nonene and 2-methyl-1-octene and its preparation method. Background Technology

[0002] Propylene trimerization is an important route for producing fine chemicals, with 1-nonene being the main trimerization product. During the preparation of 1-nonene from propylene trimerization, byproducts such as 2-methyl-1-octene are generated. Since 1-nonene and 2-methyl-1-octene have similar distillation ranges, their separation is challenging. Currently, distillation is commonly used to separate 1-nonene and 2-methyl-1-octene in order to obtain high-purity 1-nonene.

[0003] By searching the boiling point data of 1-nonene and 2-methyl-1-octene, we can see that the boiling point of 1-nonene is 145℃, and the boiling point of 2-methyl-1-octene is 142.6℃, with a difference of about 2.4℃, and their relative volatility is quite similar. If 1-nonene and 2-methyl-1-octene (containing 95% 1-nonene) are separated by conventional distillation to increase the purity of 1-nonene to 99.5%, at least 70 theoretical plates would be required. This means a huge fixed asset investment and a significant reduction in economic efficiency.

[0004] The purpose of this invention is to provide an adsorbent for the efficient separation of 1-nonene and 2-methyl-1-octene and its preparation method. Compared with conventional distillation, this method can significantly reduce the investment in fixed equipment and energy consumption required for the separation of 1-nonene, and has important economic and social benefits. Summary of the Invention

[0005] The purpose of this invention is to solve the problems of high investment and high energy consumption in conventional distillation equipment for separating 1-nonene. This invention innovatively combines transition metal salts with porous supports to prepare a highly efficient adsorbent suitable for the separation of 1-nonene and 2-methyl-1-octene. The results show that the purity of 1-nonene is improved to a certain extent compared with porous supports without transition metal salts.

[0006] In a first aspect, the present invention provides a method for preparing an adsorbent for efficiently separating 1-nonene and 2-methyl-1-octene, specifically comprising the following steps:

[0007] S1: Prepare a solution by dissolving 0.5 to 3 parts by mass of a transition metal salt in 80 to 120 parts by mass of water, and impregnate 7 to 12 parts by mass of a porous carrier.

[0008] The transition metal salt is selected from at least one of FeCl3, CuCl2, and CoCl2;

[0009] The porous support is selected from at least one of γ-Al2O3, ZIF-8, and ZIF-20;

[0010] S2: Under an inert gas atmosphere, the impregnated porous support is subjected to solvent removal treatment to obtain the adsorbent.

[0011] Preferably, in step S1, the immersion temperature is 20-50°C and the immersion time is not less than 60 minutes.

[0012] Furthermore, the impregnation temperature is 30°C.

[0013] Preferably, in step S2, the inert gas is N2 or Ar.

[0014] Furthermore, the inert gas is N2.

[0015] Preferably, in step S2, the solvent removal process is a drying process, and the drying temperature is 20℃~80℃.

[0016] Furthermore, the drying temperature is 50°C.

[0017] Preferably, the transition metal salt is CuCl2, and the porous support is ZIF-20.

[0018] In a second aspect, the present invention provides an adsorbent for efficiently separating 1-nonene and 2-methyl-1-octene, which is synthesized using the method described in the first aspect.

[0019] Thirdly, the present invention provides an application of the adsorbent described in the second aspect for the separation of 1-nonene and 2-methyl-1-octene.

[0020] The expected beneficial effects of this invention are:

[0021] The high-efficiency adsorbent of this invention can effectively separate 1-nonene and 2-methyl-1-octene, increase the concentration of 1-nonene in the mixture, and has a simple process, low equipment investment and low energy consumption, thus having significant economic and social benefits. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the following embodiments. It should be noted that this invention is not limited to the following embodiments.

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] The catalyst performance in the following examples was evaluated as follows: Adsorbent evaluation was conducted in a batch reactor. 100 mL of 1-nonene and 2-methyl-1-octene, containing 5% 2-methyl-1-octene, were injected into the reactor. The adsorption reaction was carried out under a fixed stirring speed. After 1 hour of adsorption, the reaction product was injected into a gas chromatograph, and the contents of 1-nonene and 2-methyl-1-octene in the reaction results were analyzed online. The purification effect was calculated based on the concentration of 1-nonene.

[0025] In the following examples, the catalyst is named as follows: "Metal salt type (Cu, Fe, Co) and mass parts" - "Support used (γ-Al2O3, ZIF-8, ZIF-20)" - "Impregnation temperature" - "Drying temperature" - "Protective gas type"; for example, if the catalyst preparation conditions are 15 mass parts of anhydrous CuCl2, the support is ZIF-20, the impregnation temperature is 30°C, and the activation drying temperature under nitrogen protection is 50°C, then it is named "Cu15-Z20-30-50-N2".

[0026] Example 1

[0027] Preparation of adsorbents with different transition metal salts:

[0028] ① Weigh 1.5g of anhydrous CuCl2, FeCl3, and CoCl2 respectively and impregnate them with 10.0g of ZIF-20 carrier at 30℃.

[0029] ② Under nitrogen protection, adjust the oven temperature to 50℃ and process for 2 hours.

[0030] The adsorption results of the adsorbent prepared in Example 1 are shown in Table 1.

[0031] Table 1 Test Results of Example 1

[0032] catalyst transition metal salts 1-Nonene purity (%) <![CDATA[Cu15-Z20-30-50-N2]]> <![CDATA[CuCl2]]> 98.2 <![CDATA[Fe15-Z20-30-50-N2]]> <![CDATA[FeCl3]]> 96.2 <![CDATA[Co15-Z20-30-50-N2]]> <![CDATA[CoCl2]]> 97.1

[0033] Example 2

[0034] Preparation of adsorbents with different porous supports:

[0035] The catalyst was prepared according to the synthesis method in Example 1, except that the transition metal salt was selected as CuCl2, and the porous support was selected as γ-Al2O3, ZIF-8, and ZIF-20, respectively.

[0036] The adsorption results of the adsorbent prepared by this method are shown in Table 2.

[0037] Table 2 Test Results of Example 2

[0038] catalyst Porous carrier 1-Nonene purity (%) <![CDATA[Cu15-Z20-30-50-N2]]> ZIF-20 98.2 <![CDATA[Cu15-Z8-30-50-N2]]> ZIF-8 97.8 <![CDATA[Cu15-ZA-30-50-N2]]> γ-Al2O3 97.6

[0039] Example 3

[0040] Preparation of adsorbents with different transition metal salt loadings:

[0041] The catalyst was prepared according to the synthesis method in Example 1, except that the transition metal salt was selected as CuCl2, and the amounts of the transition metal salt were 1.0 g, 1.5 g and 2.0 g, respectively.

[0042] The catalytic results of the adsorbent prepared by this method are shown in Table 3.

[0043] Table 3 Test Results of Example 3

[0044]

[0045]

[0046] Example 4

[0047] Preparation of adsorbents at different drying temperatures:

[0048] The catalyst was prepared according to the synthesis method in Example 1, except that the transition metal salt was selected as CuCl2, and the drying temperatures were selected as 20°C, 50°C, and 80°C, respectively.

[0049] The adsorption results of the adsorbent prepared by this method are shown in Table 4.

[0050] Table 4 Test Results of Example 4

[0051] catalyst Drying temperature (°C) 1-Nonene purity (%) <![CDATA[Cu15-Z20-30-50-N2]]> 50 98.2 <![CDATA[Cu15-Z20-30-20-N2]]> 20 97.6 <![CDATA[Cu15-Z20-30-80-N2]]> 80 95.4

[0052] Example 5

[0053] This invention is used to illustrate the preparation of adsorbents with different impregnation temperatures.

[0054] The catalyst was prepared according to the synthesis method in Example 1, except that the transition metal salt was selected as CuCl2, and the impregnation temperature was set to 20°C, 30°C and 50°C, respectively.

[0055] The adsorption results of the adsorbent prepared by this method are shown in Table 5.

[0056] Table 5 Test Results of Example 5

[0057]

[0058]

[0059] Example 6

[0060] This invention is used to illustrate the preparation of adsorbents for different inert gases provided by the present invention.

[0061] The catalyst was prepared according to the synthesis method in Example 1, except that the transition metal salt was selected as CuCl2, and the inert gases were selected as N2 and Ar, respectively.

[0062] The catalytic results of the catalyst prepared by this method are shown in Table 6.

[0063] Table 6 Test Results of Example 6

[0064] catalyst inert gases 1-Nonene purity (%) <![CDATA[Cu15-Z20-30-50-N2]]> <![CDATA[N2]]> 98.2 Cu15-Z20-30-50-Ar Ar 98.1

[0065] Comparative Example

[0066] Preparation of porous carrier adsorbents for illustration

[0067] The catalyst was prepared according to the method of Example 1, except that only a porous support was used as the adsorbent. 1-Nonene was separated according to the conditions of Example 1, and the purity of 1-nonene was 95.2%.

[0068] The test results above show that combining transition metal salts with porous supports under certain conditions can produce highly efficient adsorbents suitable for the separation of 1-nonene and 2-methyl-1-octene.

Claims

1. The application of an adsorbent in the separation of 1-nonene and 2-methyl-1-octene, characterized in that, The preparation method of the adsorbent specifically includes the following steps: S1: Prepare a solution by dissolving 0.5 to 3 parts by mass of a transition metal salt in 80 to 120 parts by mass of water, and impregnate 7 to 12 parts by mass of a porous carrier. The transition metal salt is selected from at least one of FeCl3, CuCl2, and CoCl2; The porous support is selected from at least one of γ-Al2O3, ZIF-8, and ZIF-20; S2: Under an N2 or Ar atmosphere, the impregnated porous support is subjected to solvent removal treatment to obtain an adsorbent; the solvent removal treatment is a drying treatment, and the drying treatment temperature is 20℃~50℃.

2. The application of the adsorbent according to claim 1 in the separation of 1-nonene and 2-methyl-1-octene, characterized in that, In step S1, the immersion temperature is 20~50℃ and the immersion time is not less than 60min.

3. The application of the adsorbent according to claim 2 in the separation of 1-nonene and 2-methyl-1-octene, characterized in that, The impregnation temperature is 30°C.

4. The application of the adsorbent according to claim 1 in the separation of 1-nonene and 2-methyl-1-octene, characterized in that, Step S2 is performed under an N2 atmosphere.

5. The application of the adsorbent according to claim 1 in the separation of 1-nonene and 2-methyl-1-octene, characterized in that, The drying temperature is 50°C.

6. The application of the adsorbent according to claim 1 in the separation of 1-nonene and 2-methyl-1-octene, characterized in that, The transition metal salt is CuCl2, and the porous support is ZIF-20.

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