Dechlorination active carrier and method for preparing the same

Abstract

The application belongs to the technical field of dechlorination carrier and specifically provides a preparation method of a dechlorination active carrier, which comprises the following steps: 1) polyoxyethylene-polyoxypropylene block copolymer and modified protein solution are dissolved in deionized water, then cobalt nitrate, aluminum lactate and 2-aldehyde benzene boronic acid are added and stirred uniformly, reaction is carried out at 110-130 DEG C, centrifugation and drying are carried out to obtain a precursor; 2) tetrabutylphosphonium hydroxide and sodium aluminate are added into deionized water, TEOS and the precursor are added after mixing, stirring is carried out, crystallization is carried out at 165-175 DEG C, centrifugation and washing are carried out, and the obtained solid is dried and calcined to obtain the dechlorination active carrier. The carrier prepared by the application has the advantage of good dechlorination effect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of dechlorination carriers, and particularly relates to a dechlorination active carrier and a preparation method thereof. BACKGROUND

[0002] In the petroleum refining industry, catalytic reforming technology plays a crucial role and provides technical support for secondary processing of crude oil. With increasing attention to the influence of chlorine corrosion in catalytic reforming devices, dechlorination processes are increasingly valued. Chlorides in crude oil mainly come from chlorinated salts and organic chlorides carried in the crude oil extraction process and artificially added chlorine-containing oil extraction additives. These chlorides will migrate to downstream products and devices during the crude oil processing, causing great harm to enterprise safety production and the environment, which has become a major problem in the industry.

[0003] Chlorides in crude oil and its distillate oil have strong polarity and are easily converted into hydrogen chloride. In the oil refining process, not only distillation equipment is corroded, but also the stability of the reforming pre-hydrogenation device, catalytic cracking device and hydrofining device is seriously affected. In addition, it also causes irreversible poisoning of the catalyst used in the refining process, and even permanent deactivation. At present, technical personnel usually use the "one removal and three injection" process to remove inorganic chlorides in crude oil, and the removal of organic chlorides mainly uses direct adsorption method, nucleophilic substitution method, catalytic hydrogenation method and electrochemical reduction dechlorination method, etc.

[0004] For the direct adsorption method, it can be divided into physical adsorption and chemical adsorption. Physical adsorption relies on intermolecular interaction for absorption, and the process is a reversible process without selectivity. Chemical adsorption is formed by chemical bonds between molecules, and the adsorption process has selectivity. Common chemical adsorbents include activated carbon, metal oxides, molecular sieves and other materials. For example, some technical personnel use alumina as a dechlorination agent carrier and noble metal as an active component to prepare a dechlorination adsorbent, which has good adsorption capacity. The adsorption performance and dechlorination effect of the dechlorination agent will directly affect the quality of oil, gas and other refined products, so it is of great practical significance to actively develop more efficient dechlorination materials. SUMMARY

[0005] In view of the above problems, in order to further improve the performance of the dechlorination agent, the application provides a dechlorination active carrier and a preparation method thereof.

[0006] The application first provides a preparation method of a dechlorination active carrier, which comprises the following steps:

[0007] 1) Dissolve polyoxyethylene-polyoxypropylene block copolymer and modified protein solution in deionized water, then add cobalt nitrate, aluminum lactate and 2-aldehyde benzene boronic acid, stir uniformly, and react at 110-130 DEG C. Centrifuge and dry to obtain a precursor;

[0008] 2) adding tetrabutylphosphonium hydroxide and sodium aluminate into deionized water, mixing, then adding TEOS and precursors, stirring, crystallizing at 165-175°C, centrifuging, washing, drying and calcining the obtained solid to obtain the product.

[0009] Further, in the step 1), the modified protein solution is prepared by the following method: adding soybean protein and polysaccharide into deionized water, dissolving thoroughly, adjusting the pH value to 7-9, then heating to react, cooling after the reaction to obtain the product.

[0010] Further, the mass ratio of the soybean protein to the polysaccharide is 1.5-2.5:1.

[0011] Further, the polysaccharide is one of xanthan gum, carrageenan and guar gum.

[0012] Further, the heating reaction is performed in the presence of choline chloride.

[0013] Further, in the step 1), the mass ratio of the polyoxyethylene-polyoxypropylene block copolymer to the modified protein solution is 1:0.15-0.2.

[0014] Further, in the step 2), the crystallization time is 48-60h.

[0015] Further, in the step 2), the mass ratio of TEOS to the precursors is 1:0.2-0.3.

[0016] Further, in the step 2), the calcination is performed at 500-600°C for 3-5h.

[0017] The application also provides a dechlorination active carrier prepared by the above method.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] The application uses polyoxyethylene-polyoxypropylene block copolymer, modified protein solution, cobalt nitrate, aluminum lactate and 2-aldehyde benzene boronic acid to prepare precursors of layered coating structure, then crystallizes the precursors, sodium aluminate and TEOS under the action of tetrabutylphosphonium hydroxide, and forms an active carrier with high specific surface area and excellent pore structure after calcination, thereby providing larger adsorption surface area and more adsorption sites, improving the mass transfer rate and obtaining better dechlorination effect. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The figure is the carrier dechlorination performance test data graph of the examples 1-3 and the control groups 1-2 of the application.

[0021] Figure 2Figure 1 shows the dechlorination adsorption isotherm equation parameters of the carriers in the examples 1-3 and the control groups 1-2 of the present application. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described in combination with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0023] The present application provides a preparation method of a dechlorination active carrier through a large number of experimental researches, which comprises the following steps:

[0024] 1) Dissolve polyoxyethylene-polyoxypropylene block copolymer and modified protein solution in deionized water, then add cobalt nitrate, aluminum lactate and 2-aldehyde benzene boronic acid, stir uniformly, react at 110-130°C, centrifuge and dry to obtain a precursor;

[0025] 2) Add tetrabutylphosphonium hydroxide and sodium aluminate to deionized water, then add TEOS and the precursor after mixing, stir, crystallize at 165-175°C, centrifuge, wash, and dry and calcine the obtained solid to obtain the dechlorination active carrier.

[0026] Further, in the step 1), the modified protein solution is prepared by the following method: add soybean protein and polysaccharide to deionized water, fully dissolve, adjust the pH value to 7-9, then heat and react, and obtain after cooling.

[0027] Further, the mass ratio of the soybean protein to the polysaccharide is 1.5-2.5:1.

[0028] In some specific embodiments, the mass ratio of the soybean protein to the polysaccharide can be 1.5-1.8:1, 1.8-2.0:1, 2.0-2.2:1, 2.2-2.5:1. Further preferably, the mass ratio of the soybean protein to the polysaccharide can be 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1. In general, the mass ratio of the soybean protein to the polysaccharide is 2:1, which can achieve better results.

[0029] Further, the polysaccharide is one of xanthan gum, carrageenan and guar gum.

[0030] Further, choline chloride is also added during the heating reaction.

[0031] Further, in the step 1), the mass ratio of the polyoxyethylene-polyoxypropylene block copolymer and the modified protein solution can be 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19, or 1:0.2. In general, the mass ratio of the polyoxyethylene-polyoxypropylene block copolymer and the modified protein solution in the step 1) is 1:0.2, and better results can be achieved.

[0032] Further, in the step 1), the mass ratio of the polyoxyethylene-polyoxypropylene block copolymer and the modified protein solution can be 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19, or 1:0.2. In general, the mass ratio of the polyoxyethylene-polyoxypropylene block copolymer and the modified protein solution in the step 1) is 1:0.2, and better results can be achieved.

[0033] Further, in the step 2), the crystallization time is 48-60h.

[0034] Further, in the step 2), the mass ratio of TEOS and the precursor is 1:0.2-0.3.

[0035] In some embodiments, the mass ratio of TEOS and the precursor in the step 2) can be 1:0.2, 1:0.21, 1:0.22, 1:0.23, 1:0.24, 1:0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.29, or 1:0.3. In general, the mass ratio of TEOS and the precursor in the step 2) is 1:0.25, and better experimental results can be achieved.

[0036] Further, in the step 2), the calcination is performed at a temperature of 500-600℃ for 3-5h.

[0037] The application will be further described by the following examples, but the scope of the application is not limited by the examples.

[0038] Example 1

[0039] The preparation method of the dechlorination active carrier of the present embodiment comprises the following steps:

[0040] 1) 20g of polyoxyethylene-polyoxypropylene block copolymer (pluronic F127, Mv=12600g / mol), 4g of modified protein solution were dissolved in 1500mL of deionized water, then 14.55g of cobalt nitrate hexahydrate, 4.38g of aluminum lactate, and 1.5g of 2-aldehyde benzene boronic acid were added, stirred for 1h, and then transferred to a reaction kettle, reacted at 115℃ for 24h, cooled, centrifuged, and the obtained product was washed and dried to obtain a precursor;

[0041] 2) Into 100 mL of deionized water, 0.05 mol of tetrabutylphosphonium hydroxide and 0.065 g of sodium aluminate were added, after mixing, 8.27 g of TEOS and 2 g of the precursor were added, after stirring, it was transferred into a stainless steel autoclave with a polytetrafluoroethylene liner, crystallized at 170°C for 48 h, the obtained precipitate was centrifuged, washed with deionized water, the obtained solid was dried, calcined at a temperature of 550°C for 4 h in an air atmosphere, and then ST-2 was obtained.

[0042] The modified protein solution of the present example was prepared by the following steps: 2 g of soybean protein isolate and 1 g of polysaccharide (xanthan gum) were added to 100 mL of deionized water, and after being fully dissolved, the pH value was adjusted to 9, and then heated in a water bath at 90°C for 1 h, and then cooled with an ice water bath after the reaction was completed.

[0043] Example 2

[0044] The preparation method of the dechlorination active carrier of the present example comprises the following steps:

[0045] 1) 20 g of polyoxyethylene-polyoxypropylene block copolymer (pluronic F127, Mv=12600 g / mol), 4 g of modified protein solution were dissolved in 1500 mL of deionized water, then 14.55 g of cobalt nitrate hexahydrate, 4.38 g of aluminum lactate, and 1.5 g of 2-aldehyde benzene boronic acid were added, stirred for 1 h, and then transferred into a reaction kettle, reacted at 115°C for 24 h, cooled, centrifuged, washed and dried to obtain the precursor;

[0046] 2) Into 100 mL of deionized water, 0.05 mol of tetrabutylphosphonium hydroxide and 0.065 g of sodium aluminate were added, after mixing, 8.27 g of TEOS and 2 g of the precursor were added, after stirring, it was transferred into a stainless steel autoclave with a polytetrafluoroethylene liner, crystallized at 170°C for 48 h, the obtained precipitate was centrifuged, washed with deionized water, the obtained solid was dried, calcined at a temperature of 550°C for 4 h in an air atmosphere, and then ST-2 was obtained.

[0047] The modified protein solution of the present example was prepared by the following steps: 2 g of soybean protein isolate and 1 g of polysaccharide (xanthan gum) were added to 100 mL of deionized water, and after being fully dissolved, the pH value was adjusted to 9, and then heated in a water bath at 90°C for 1 h, and then cooled with an ice water bath after the reaction was completed.

[0048] Example 3

[0049] The preparation method of the dechlorination active carrier of the present example comprises the following steps:

[0050] 1) 20 g of polyoxyethylene-polyoxypropylene block copolymer (pluronic F127, Mv = 12600 g / mol), 4 g of modified protein solution were dissolved in 1500 mL of deionized water, then 14.55 g of cobalt nitrate hexahydrate, 4.38 g of aluminum lactate, 1.5 g of 2-aldehyde benzene boronic acid were added, stirred for 1 h, then transferred to a reaction kettle, reacted at 115°C for 24 h, cooled, centrifuged, and the product obtained by centrifugation was washed, dried to obtain a precursor;

[0051] 2) 0.05 mol of tetrabutylphosphonium hydroxide and 0.065 g of sodium aluminate were added to 100 mL of deionized water, mixed, then 8.27 g of TEOS and 2 g of the precursor were added, stirred, then transferred to a stainless steel autoclave with a polytetrafluoroethylene liner, crystallized at 170°C for 48 h, the precipitate was centrifuged, washed with deionized water, and the solid was dried and calcined at 550°C in air for 4 h to obtain ST-3.

[0052] The modified protein solution of this example was prepared by the following steps: 2 g of soybean protein isolate and 1 g of polysaccharide (xanthan gum) were added to 100 mL of deionized water, dissolved thoroughly, then the pH value was adjusted to 9, then heated in a water bath at 90°C for 30 min, then 0.2 g of choline chloride was added, and the reaction was continued for 30 min, then cooled with an ice water bath to obtain the modified protein solution.

[0053] Control group 1

[0054] The preparation method of the dechlorination active carrier of this control group comprises the following steps: 0.05 mol of tetrabutylphosphonium hydroxide and 0.065 g of sodium aluminate were added to 100 mL of deionized water, mixed, then 8.27 g of TEOS was added, stirred, then transferred to a stainless steel autoclave with a polytetrafluoroethylene liner, crystallized at 170°C for 48 h, the precipitate was centrifuged, washed with deionized water, and the solid was dried and calcined at 550°C in air for 4 h to obtain ST-5.

[0055] Control group 2

[0056] The preparation method of the dechlorination active carrier of this control group comprises the following steps:

[0057] 1) 20 g of polyoxyethylene-polyoxypropylene block copolymer (pluronic F127, Mv = 12600 g / mol), 4 g of modified protein solution were dissolved in 1500 mL of deionized water, then 14.55 g of cobalt nitrate hexahydrate, 4.38 g of aluminum lactate, 1.5 g of 2-aldehyde benzene boronic acid were added, stirred for 1 h, then transferred to a reaction kettle, reacted at 115°C for 24 h, cooled, centrifuged, and the product obtained by centrifugation was washed, dried to obtain a precursor;

[0058] 2) To 100 mL of deionized water, 0.05 mol of tetrabutylphosphonium hydroxide and 0.065 g of sodium aluminate were added, after mixing, 8.27 g of TEOS and 2 g of the precursor were added, after stirring, it was transferred into a stainless steel autoclave with a polytetrafluoroethylene liner, crystallized at 170°C for 48 h, the obtained precipitate was centrifuged, washed with deionized water, the obtained solid was dried, calcined at a temperature of 550°C for 4 h in an air atmosphere, and then ST-5 was obtained.

[0059] Performance detection

[0060] Static adsorption experiments were carried out on the carriers of Examples 1-3 and Control Examples 1-2, and the conditions were set as follows: adsorption temperature 333.15 K, adsorption time 50-300 min, initial concentration of 1,2-dichloroethane 98.21 mg / L, and solvent / oil ratio 1 g:40 mL. The specific experimental results are shown in Table 1. Figure 1 The Langmuir adsorption isotherm equation parameters of the carriers can be obtained through the static adsorption experiments, q L is the adsorption amount (mg / g), K L is the adsorption equilibrium constant (L / mg), R 2 is the determination coefficient. As shown in Table 2, the carrier of the present application has very good adsorption and dechlorination effect. Figure 2

[0061] Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements to part of the technical features, and any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.​

Claims

1. A method for preparing a dechlorination active support, characterized by: It comprises the following steps: 1) dissolving polyoxyethylene-polyoxypropylene block copolymer and modified protein solution in deionized water, then adding cobalt nitrate, aluminum lactate and 2-aldehyde benzene boronic acid, stirring uniformly, reacting at 110-130℃, centrifuging and drying to obtain the precursor; the modified protein solution is prepared by the following method: adding soybean protein and polysaccharide into deionized water, dissolving thoroughly, adjusting pH value to 7-9, then heating to react, cooling after reaction to obtain the solution; the polysaccharide is one of xanthan gum, carrageenan and guar gum; 2) adding tetrabutylphosphonium hydroxide and sodium aluminate into deionized water, mixing, then adding TEOS and the precursor, stirring, crystallizing at 165-175℃, centrifuging, washing, drying and calcining the obtained solid to obtain the product.

2. The method of claim 1, wherein: The mass ratio of soybean protein to polysaccharide is 1.5-2.5:

1.

3. The method for preparing the dechlorination active carrier according to claim 1, characterized in that: Choline chloride is also added during the heating reaction.

4. The method for preparing the dechlorination active carrier according to claim 1, characterized in that: In step 1), the mass ratio of polyoxyethylene-polyoxypropylene block copolymer to modified protein solution is 1:0.15-0.

2.

5. The method of claim 1, wherein: In step 2), the crystallization time is 48-60h.

6. The method of claim 1, wherein: In step 2), the mass ratio of TEOS to the precursor is 1:0.2-0.

3.

7. The method of claim 1, wherein: In step 2), the calcination is carried out at 500-600℃ for 3-5h.

8. A dechlorination active support, characterized by: The product is prepared by the preparation method of any one of claims 1-7.

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