Methods for improving the color of high melting point Fischer-Tropsch wax and refined Fischer-Tropsch wax products

Abstract

This invention relates to the field of Fischer-Tropsch wax refining, and discloses a method for improving the color of high-melting-point Fischer-Tropsch wax and a refined Fischer-Tropsch wax product. The method of this invention includes: (1) mixing a material containing a first additive with Fischer-Tropsch wax raw material to obtain a first mixture; (2) mixing an activator containing a second additive with a decolorizing agent containing an adsorbent to obtain a second mixture; (3) mixing the first mixture and the second mixture for adsorption to obtain a molten mixture system; (4) performing a first solid-liquid separation on the molten mixture system to obtain a first filter cake and a refined wax liquid; (5) distilling the refined wax liquid to obtain a recovery liquid and a refined Fischer-Tropsch wax product; wherein, in step (3), the adsorption conditions are: temperature 90-130℃, time 30-60min; the first additive and the second additive are both polar organic compounds. The method of this invention can obtain a refined Fischer-Tropsch wax product with a high cerété color and fewer impurities.

Description

Technical Field

[0001] This invention relates to the field of Fischer-Tropsch wax refining, specifically to a method for improving the color of high-melting-point Fischer-Tropsch wax and a refined Fischer-Tropsch wax product. Background Technology

[0002] High-melting-point Fischer-Tropsch waxes are widely used in gloss waxes, textile auxiliaries, hot melt adhesives, inks and coatings, plastics processing, food, and cosmetics. Improving the color of high-melting-point Fischer-Tropsch waxes can broaden their application range and enhance their value. High-melting-point Fischer-Tropsch waxes are mainly available in granular or powder form, composed of straight-chain, saturated high-carbon alkanes with a carbon number distribution of C40-C80 and a relative molecular mass of 500 g / mol-1000 g / mol. This gives this special chemical a fine crystal structure, high melting point (generally above 80℃), narrow melting point range, low oil content, low penetration, low migration, very low melt viscosity, high stability, and characteristics such as hardness and wear resistance. Compared to low-melting-point Fischer-Tropsch waxes, high-melting-point waxes require higher temperatures to melt, and methods used for decolorizing low-melting-point Fischer-Tropsch waxes are ineffective for decolorizing high-melting-point Fischer-Tropsch waxes. Furthermore, at higher adsorption temperatures (≥140℃), the use of activated clay can cause a deterioration reaction in high-melting-point Fischer-Tropsch waxes, thereby deepening their color. Therefore, the methods disclosed in existing inventions are mainly designed for paraffin waxes, phase change waxes, or Fischer-Tropsch waxes with lower melting points and are not suitable for decolorizing and upgrading high-melting-point Fischer-Tropsch waxes.

[0003] CN201510880963.X discloses a method for improving the color of Fischer-Tropsch wax, which combines continuous high-vacuum distillation and adsorption purification, using activated clay as an adsorbent to improve the color value of Fischer-Tropsch wax. This method has the advantage of high decolorization efficiency, but the adsorption temperature requirement is relatively high, which can easily cause high-melting-point Fischer-Tropsch wax to deteriorate under the action of activated clay.

[0004] CN202011604777.0 discloses a method for decolorizing Fischer-Tropsch wax. Based on the adsorption and purification of activated clay and waste MTP catalyst, a separation liquid is added for aging and filtration. The resulting refined Fischer-Tropsch wax has a color number of about 3. The decolorization effect of this method needs to be improved and requires the addition of a separation liquid for synergistic effect. The entire decolorization cycle is long.

[0005] CN200910062097.8 discloses a method for decolorizing phase change wax. This invention uses a multi-stage adsorption filtration method, using activated clay as an adsorbent to directly mix with the phase change wax for adsorption purification. This process is relatively simple; however, this method is only suitable for decolorizing Fischer-Tropsch wax with a low melting point. For Fischer-Tropsch wax with a high melting point, the decolorization effect will be poor or the color will return. In addition, the activated clay cannot be regenerated in hot water.

[0006] Therefore, it is necessary to study a method to improve the color of high-melting-point Fischer-Tropsch wax. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of easy color reversion during decolorization of high-melting-point Fischer-Tropsch wax, excessively high decolorization temperature, cumbersome decolorization process, and high investment cost in the existing technology. This invention provides a method for improving the color of high-melting-point Fischer-Tropsch wax and a refined Fischer-Tropsch wax product. This method is simple in process. Through the synergistic effect of a decolorizing agent containing an adsorbent, a material containing a first auxiliary agent, and an activator containing a second auxiliary agent, (1) the temperature required for melting high-melting-point Fischer-Tropsch wax can be reduced, promoting wax melting and reducing wax deposition on the adsorbent surface; (2) the adsorbent is pre-activated, improving adsorption efficiency, effectively removing impurities from the Fischer-Tropsch wax raw material, preventing color reversion in the refined Fischer-Tropsch wax product at high temperatures, and improving the use value of the refined Fischer-Tropsch wax product, resulting in higher economic and social benefits. The method of this invention can effectively improve the color of the obtained high-melting-point Fischer-Tropsch wax, resulting in a refined Fischer-Tropsch wax product with a higher sepia color and fewer impurities.

[0008] To achieve the above objectives, a first aspect of the present invention provides a method for improving the color intensity of high-melting-point Fischer-Tropsch wax, the method comprising:

[0009] (1) The material containing the first additive is mixed with the Fischer-Tropsch wax raw material to obtain a first mixture;

[0010] (2) The activator containing the second auxiliary agent and the decolorizing agent containing the adsorbent are mixed for the second time to obtain the second mixture;

[0011] (3) The first mixture and the second mixture are mixed for adsorption to obtain a melt-mixed system;

[0012] (4) The melt-mixed system is subjected to a first solid-liquid separation to obtain a first filter cake and refined wax liquid;

[0013] (5) Distill the refined wax liquid to obtain the recovered liquid and refined Fischer-Tropsch wax products;

[0014] In step (3), the adsorption conditions are: temperature of 90-130℃ and time of 30-60min.

[0015] Both the first and second additives are polar organic compounds.

[0016] A second aspect of the present invention provides a refined Fischer-Tropsch wax product obtained by the above method.

[0017] The beneficial effects obtained by the present invention through the above technical solution are as follows:

[0018] 1. In the method of the present invention, the removal efficiency of impurities is high, the decolorization effect of high melting point Fischer-Tropsch wax is good, and the color return phenomenon of high melting point wax can be effectively avoided; the inorganic matter in the final refined Fischer-Tropsch wax product is removed to below 10 ppm.

[0019] 2. This invention does not require hydrogenation refining or multi-stage adsorption filtration, yet it can effectively improve product color. It has low energy consumption and low equipment investment, simple process, good decolorization effect, and high economic efficiency.

[0020] 3. The adsorbents used in this invention, such as activated clay, are widely available and inexpensive.

[0021] 4. The method of the present invention can be used to decolorize Fischer-Tropsch wax raw materials of various color numbers, especially for Fischer-Tropsch wax raw materials with a Cyper Special number <-16.

[0022] 5. In a preferred embodiment, the method of the present invention further includes the recovery of the first auxiliary agent and the second auxiliary agent, as well as the regeneration of the adsorbent. The regenerated adsorbent can be reused, which significantly reduces the amount of adsorbent such as activated clay used in the entire decolorization process and reduces environmental pollution. Attached Figure Description

[0023] Figure 1 A process flow diagram of a method for improving the color intensity of high melting point Fischer-Tropsch wax provided by the present invention;

[0024] Figure 2 The present invention provides a process flow diagram for another method to improve the color of high melting point Fischer-Tropsch wax. Detailed Implementation

[0025] 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.

[0026] The first aspect of the present invention provides a method for improving the color intensity of high-melting-point Fischer-Tropsch wax, the method comprising:

[0027] (1) The material containing the first additive is mixed with the Fischer-Tropsch wax raw material to obtain a first mixture;

[0028] (2) The activator containing the second auxiliary agent and the decolorizing agent containing the adsorbent are mixed for the second time to obtain the second mixture;

[0029] (3) The first mixture and the second mixture are mixed for adsorption to obtain a melt-mixed system;

[0030] (4) The melt-mixed system is subjected to a first solid-liquid separation to obtain a first filter cake and refined wax liquid;

[0031] (5) Distill the refined wax liquid to obtain the recovered liquid and refined Fischer-Tropsch wax products;

[0032] In step (3), the adsorption conditions are: temperature of 90-130℃ and time of 30-60min.

[0033] Both the first and second additives are polar organic compounds.

[0034] In this invention, when the adsorption conditions are not within the above range, excessively high temperature or excessively long adsorption time will cause the wax liquid to undergo a deterioration reaction, resulting in a low color of the refined Fischer-Tropsch wax product. When the temperature is too low, the raw wax may not dissolve completely, and when the adsorption time is too short, the adsorbent may not adsorb impurities completely. Both of these will result in poor decolorization effect of the adsorbent, resulting in a low color of the refined Fischer-Tropsch wax product.

[0035] In this invention, the adsorption method can be selected using conventional techniques in the art. For example, the adsorption can be performed by mixing the first mixture and the second mixture, placing the mixture in a reaction vessel at 90-130°C, and stirring for 30-60 minutes.

[0036] The inventors discovered that by mixing an activator containing a second additive with a decolorizing agent containing an adsorbent, and using the second additive to pre-activate the adsorbent, especially activated clay, the decolorization effect and filtration efficiency of high-melting-point Fischer-Tropsch wax can be greatly improved, while also preventing the final refined Fischer-Tropsch wax product from reverting to its original color.

[0037] In this invention, the first filter cake mainly contains waste adsorbent.

[0038] In this invention, the recovered liquid is a mixture of the first auxiliary agent and the second auxiliary agent obtained after distillation, which can be added to the material containing the first auxiliary agent in step (1) or to the activator in step (2).

[0039] In some embodiments of the present invention, the recovered liquid can be divided into three parts. Preferably, the method further includes: adding the first part of the recovered liquid obtained in step (5) to the material in step (1), adding the second part to the activator in step (2), and using the third part to wash the first filter cake obtained in step (4); after washing, a second solid-liquid separation is performed to obtain a second filter cake. The washing process can regenerate the waste adsorbent contained in the first filter cake, and the resulting second filter cake mainly contains the regenerated adsorbent. The washing process can be a conventional technique in the art, such as mixing and heating the recovered liquid with the first filter cake. Preferably, the washing temperature is 90-120°C, and the washing time is 10-20 minutes. The amount of recovered liquid used in the washing process is not limited, as long as it is sufficient to fully wash the first filter cake. Those skilled in the art can choose according to the actual situation, and this will not be elaborated further here. Preferably, the second filter cake can be added to the decolorizing agent in step (2).

[0040] In some embodiments of the present invention, the recovery rate of the regenerated adsorbent in the second filter cake is not less than 99%.

[0041] Wherein, the recovery rate of the regenerated adsorbent = weight of the regenerated adsorbent in the second filter cake / weight of the adsorbent in step (2) × 100%.

[0042] In this invention, "high melting point Fischer-Tropsch wax" refers to Fischer-Tropsch wax with a melting point ≥ 80°C. In some embodiments of this invention, the Fischer-Tropsch wax raw material is a high melting point Fischer-Tropsch wax with poor color and a melting point greater than 80°C, such as high melting point Fischer-Tropsch wax with melting point grades of 90#, 100#, 105#, and 110#.

[0043] In some embodiments of the present invention, the melting point of the Fischer-Tropsch wax raw material is ≥80°C.

[0044] In some embodiments of the present invention, the Fischer-Tropsch wax raw material has a cerbo denominator number < -16. The lower the cerbo denominator number, the worse the color of the Fischer-Tropsch wax raw material.

[0045] In this invention, the cerbott colorimetric value is determined using a K13190 Cebert colorimeter according to the standard GB / T 3555-92. Specifically, "cerbott colorimetric value < -16" means that when the sample tube is filled with the sample to be tested, and the sample is discharged, if the liquid column height is 53 mm, and the color of the sample observed through the eyepiece is still darker than the standard color chart, then the colorimetric value of the sample to be tested is less than -16.

[0046] It should be noted that, in this invention, the Fischer-Tropsch wax raw material's cerbo specialty number <-16 is mainly intended to describe the color difference of the Fischer-Tropsch wax raw material.

[0047] In some embodiments of the present invention, the first auxiliary agent and the second auxiliary agent are each independently selected from at least one of alcoholic organic compounds, ester organic compounds, and ketone organic compounds. When the first and second auxiliary agents are selected from the above-mentioned polar organic compounds, the method can further improve the color of high-melting-point Fischer-Tropsch wax.

[0048] In some embodiments of the present invention, the alcoholic organic compound is at least one selected from n-propanol, n-butanol, isobutanol, 1-pentanol, isoamyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, sec-octanol, and isooctanol.

[0049] In some embodiments of the present invention, the ester organic compound is at least one selected from ethyl acetate, ethyl propionate, butyl acetate, ethyl butyrate, n-propyl acetate, isopropyl acetate, isobutyl acetate, and isooctyl acetate.

[0050] In some embodiments of the present invention, the ketone organic compound is at least one selected from butanone, 2-pentanone, 3-pentanone, 3,3-dimethyl-2-butanone, diethyl methyl ketone, 3-methyl-2-pentanone, methyl isobutyl ketone, methyl sec-butyl ketone, cyclobutanone, benzophenone, and isophorone.

[0051] In some embodiments of the present invention, the adsorbent is activated clay and / or activated carbon.

[0052] In some embodiments of the present invention, the activated carbon is coal-based activated carbon and / or coconut shell activated carbon.

[0053] In this invention, step (1) is the wax melting stage, in which the Fischer-Tropsch wax raw material and the material containing the first additive are mixed evenly through the first mixing, and the Fischer-Tropsch wax raw material is completely melted to obtain the first mixture, which is the completely melted wax liquid system.

[0054] In some embodiments of the present invention, the first mixing condition is a temperature of 90-120°C. In the present invention, there is no particular limitation on the first mixing time, as long as the Fischer-Tropsch wax raw material is completely melted and completely mixed with the material containing the first additive. Preferably, the first mixing time is 15-30 minutes.

[0055] In this invention, the first mixing can be selected using conventional techniques in the art, such as stirring. For example, the first mixing can be: placing the Fischer-Tropsch wax raw material and the material containing the first additive in a reaction vessel at 90-120°C and stirring magnetically for 15-30 minutes.

[0056] In this invention, step (2) is the pre-activation stage of the adsorbent. The decolorizing agent and the activator are mixed evenly through the second mixing to obtain the second mixture, which is the adsorbent activation system.

[0057] In some embodiments of the present invention, the conditions for the second mixing are: a temperature of 90-110°C and a time of 5-30 min.

[0058] In this invention, the second mixing can be selected using conventional techniques in the art, such as stirring. For example, the second mixing can be achieved by placing the decolorizing agent and the activating agent in a reaction vessel at 90-110°C and stirring for 5-30 minutes.

[0059] In some embodiments of the present invention, in step (4), the temperature of the first solid-liquid separation is 90-130°C.

[0060] In this invention, both the first and second solid-liquid separation methods are conventional techniques in the art, such as high-speed centrifugation and filtration. The filtration method is a conventional technique in the art, such as pressure filtration and vacuum filtration. For example, the pressure filtration can be performed under nitrogen protection using a stainless steel jacketed insulated filter to separate the waste adsorbent and refined wax liquid.

[0061] In this invention, step (5) is a separation stage, in which the refined wax liquid is distilled to obtain a recovered liquid and a refined Fischer-Tropsch wax product. The refined Fischer-Tropsch wax product contains refined Fischer-Tropsch wax, additives, and inorganic impurities, wherein the additives are a mixture of a material containing a first additive and an activator containing a second additive. Preferably, the additives are a mixture of the first and second additives. Based on the total weight of the refined Fischer-Tropsch wax product, the content of additives in the refined Fischer-Tropsch wax product is no more than 0.1% by weight.

[0062] In some embodiments of the present invention, the recovery rate of the recovered liquid in step (5) is ≥99.5%.

[0063] The recovery rate of the recovered liquid refers to the ratio of the weight of the recovered liquid to the total weight of the material containing the first auxiliary agent in step (1) and the activator containing the second auxiliary agent in step (2).

[0064] In this invention, the distillation in step (5) is a conventional operation in the art and is not particularly limited. In some embodiments of this invention, the distillation is sufficient to ensure that the recovery rate of the recovered liquid is ≥99.5% and the content of additives in the refined Fischer-Tropsch wax product is ≤0.1% by weight (based on the total weight of the refined Fischer-Tropsch wax product). Preferably, the distillation is vacuum distillation, such as vacuum distillation, rotary evaporation, or vacuum flash evaporation. The conditions and methods of vacuum distillation are well known to those skilled in the art.

[0065] In some embodiments of the present invention, the mass ratio of the Fischer-Tropsch wax raw material to the material is 1:1-4. Preferably, in order to further improve the color of the refined Fischer-Tropsch wax product, the mass ratio of the Fischer-Tropsch wax raw material to the material is 1:2-3.

[0066] In some embodiments of the present invention, the mass ratio of the decolorizing agent to the activator is 1:1-2.

[0067] In some embodiments of the present invention, the amount of the decolorizing agent is 2-20 parts by weight relative to 100 parts by weight of Fischer-Tropsch wax raw material. For example, the amount of the decolorizing agent relative to 100 parts by weight of Fischer-Tropsch wax raw material can be any one of 2 parts by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 18 parts by weight, or 20 parts by weight, or a value within a range of any two of the above values. Preferably, in order to further improve the color of the obtained refined Fischer-Tropsch wax product, the amount of the decolorizing agent is 5-10 parts by weight relative to 100 parts by weight of Fischer-Tropsch wax raw material.

[0068] In some preferred embodiments of the present invention, such as Figure 2 As shown, the method includes:

[0069] (1) The first additive is mixed with Fischer-Tropsch wax raw material to obtain a first mixture;

[0070] (2) The second auxiliary agent and the adsorbent are mixed for a second time to obtain a second mixture;

[0071] (3) The first mixture and the second mixture are mixed for adsorption to obtain a melt-mixed system;

[0072] (4) The melt-mixed system is subjected to a first solid-liquid separation to obtain a first filter cake and refined wax liquid;

[0073] (5) Distill the refined wax liquid to obtain the recovered liquid and refined Fischer-Tropsch wax products;

[0074] In step (3), the adsorption conditions are: temperature of 90-130℃ and time of 30-60min.

[0075] Both the first and second additives are polar organic compounds;

[0076] Preferably, the Fischer-Tropsch wax raw material is a high-melting-point Fischer-Tropsch wax with poor color and a melting point greater than 80°C, such as high-melting-point Fischer-Tropsch wax with melting point grades of 90#, 100#, 105#, and 110#.

[0077] Preferably, the melting point of the Fischer-Tropsch wax raw material is ≥80℃;

[0078] Preferably, the Fischer-Tropsch wax raw material has a Cyperi number < -16;

[0079] Preferably, the first and second auxiliaries are independently selected from at least one of alcohols, esters, and ketones.

[0080] Preferably, the alcoholic organic compound is at least one selected from n-propanol, n-butanol, isobutanol, 1-pentanol, isoamyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, sec-octanol, and isooctanol;

[0081] Preferably, the ester organic compound is at least one selected from ethyl acetate, ethyl propionate, butyl acetate, ethyl butyrate, n-propyl acetate, isopropyl acetate, isobutyl acetate, and isooctyl acetate.

[0082] Preferably, the ketone organic compound is at least one selected from butanone, 2-pentanone, 3-pentanone, 3,3-dimethyl-2-butanone, diethyl ketone, 3-methyl-2-pentanone, methyl isobutyl ketone, methyl sec-butyl ketone, cyclobutanone, benzophenone, and isophorone;

[0083] Preferably, the adsorbent is activated clay and / or activated carbon;

[0084] Preferably, the activated carbon is coal-based activated carbon and / or coconut shell activated carbon;

[0085] Preferably, the conditions for the first mixing are: temperature of 90-120℃ and time of 15-30 min;

[0086] Preferably, the conditions for the second mixing are: a temperature of 90-110°C and a time of 5-30 minutes;

[0087] Preferably, in step (4), the temperature of the first solid-liquid separation is 90-130℃.

[0088] Preferably, the recovery rate of the recovered liquid in step (5) is ≥99.5%, and the content of additives in the refined Fischer-Tropsch wax product is ≤0.1% by weight (based on the total weight of the refined Fischer-Tropsch wax product);

[0089] The recovery rate of the recovered liquid refers to the ratio of the weight of the recovered liquid to the total weight of the first auxiliary agent in step (1) and the second auxiliary agent in step (2);

[0090] Preferably, the mass ratio of the Fischer-Tropsch wax raw material to the first additive is 1:1-4, and more preferably 1:2-3.

[0091] Preferably, the mass ratio of the adsorbent to the second auxiliary agent is 1:1-2;

[0092] Preferably, the amount of adsorbent used is 2-20 parts by weight, more preferably 5-10 parts by weight, relative to 100 parts by weight of Fischer-Tropsch wax raw material.

[0093] A second aspect of the present invention provides a refined Fischer-Tropsch wax product obtained by the above method.

[0094] In some embodiments of the present invention, the refined Fischer-Tropsch wax product has a Cyperi number ≥ +13, a melting point greater than 80°C, and an inorganic content ≤ 10 ppm.

[0095] The inorganic content is ≤10ppm, based on the total weight of the refined Fischer-Tropsch wax product.

[0096] In this invention, the Cyper Special number of the refined Fischer-Tropsch wax product was determined using a K13190 Cyper colorimeter in accordance with GB / T 3555-92 standard; the inorganic content was determined by inductively coupled plasma emission spectrometer (ICP-AES).

[0097] The present invention will be described in detail below through embodiments.

[0098] In the following examples, unless otherwise specified, all reagents and raw materials used are commercially available, and all methods used are conventional methods in the art.

[0099] In the following examples, the activated clay was sourced from Long'an County, Guangxi Province. The average pore size of the activated clay was 3.24 nm, and its specific surface area was 283 m². 2 / g.

[0100] The coal-based activated carbon used was purchased from Shanghai Yuansen Activated Carbon Co., Ltd. The average pore size of the coal-based activated carbon was 1.92 nm, and the specific surface area was 867 m². 2 / g.

[0101] In the following embodiments, unless otherwise specified, the filtration and separation method is pressure filtration, the filtration equipment is a stainless steel jacketed insulated filter, the filter cloth used is made of polytetrafluoroethylene, the filter cloth pore size is 12μm, the method is pressure filtration, and the nitrogen pressure is 0.3Mpa.

[0102] In the following examples, the color codes of refined Fischer-Tropsch wax products and Fischer-Tropsch wax raw materials refer to the Cebert color code, which is determined using a K13190 Cebert colorimeter, with reference standard GB / T 3555-92. The detection limit of the color code is -16. To determine the color code, the sample tube is filled with the sample to be tested, and then the sample is discharged. When the liquid column height of the sample reaches 53 mm, if the color of the sample observed through the eyepiece is still darker than the standard color plate, the color code is considered <-16.

[0103] The inorganic content in Fischer-Tropsch raw materials and refined Fischer-Tropsch products was determined by inductively coupled plasma atomic emission spectrometry (ICP-AES).

[0104] The content of additives in refined Fischer-Tropsch wax products was determined by oven drying loss method: 10g of the obtained refined Fischer-Tropsch wax product was weighed and placed in an oven. The oven temperature was set 5°C higher than the boiling point of the additives contained in the refined Fischer-Tropsch wax product. The product was dried at a constant temperature for 8 hours. The Fischer-Tropsch wax product was then removed and weighed, and the weight was recorded as the weight of the dried refined Fischer-Tropsch wax product. When the additives are a mixture (i.e., the first and second additives are different substances), the boiling point of the additive refers to the boiling point of the additive with the higher boiling point. For example, in Example 1, the additives contained in the refined Fischer-Tropsch wax product were a mixture of butyl acetate (boiling point 125-126°C) and isobutyl acetate (boiling point 118°C), and the oven temperature was set 5°C higher than the boiling point of butyl acetate.

[0105] Additive content = (1 - weight of dried refined Fischer-Tropsch wax product / 10g of refined Fischer-Tropsch wax product) × 100%

[0106] In the following examples, the physical properties of the Fischer-Tropsch wax raw materials used are shown in Table 1.

[0107] Table 1

[0108] Melting point grade Color number 90# Fischer-Tropsch wax raw material 90# <-16 100# Fischer-Tropsch wax raw material 100# <-16 105# Fischer-Tropsch wax raw material 105# <-16 110# Fischer-Tropsch wax raw material 110# <-16

[0109] Yield of refined Fischer-Tropsch wax product = (weight of refined Fischer-Tropsch wax product / weight of Fischer-Tropsch wax raw material) × 100%.

[0110] In the following embodiments, Examples 1-7 are performed according to Figure 2 The process flow diagram shown is followed.

[0111] Example 1

[0112] (1) Take 100g of 110# Fischer-Tropsch wax raw material and 300g of butyl acetate and mix them. Heat to 120℃ until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with butyl acetate (about 15min) to obtain a completely melted wax liquid system (i.e. the first mixture).

[0113] (2) Mix 5g of activated clay and 10g of isobutyl acetate, stir at 110℃ for 10min to pre-activate the activated clay and obtain the adsorbent activation system (i.e. the second mixture).

[0114] (3) Mix the completely melted wax system and the adsorbent activation system, and stir the adsorption reaction for 30 minutes at a stirring adsorption temperature of 120°C to obtain a molten mixed system.

[0115] (4) The molten mixture system is filtered at 110°C to obtain refined wax liquid and filter cake containing waste activated clay (i.e. waste adsorbent) (i.e. the first filter cake).

[0116] (5) The refined wax liquid was subjected to vacuum flash evaporation to obtain the recovered liquid (309g) and the refined Fischer-Tropsch wax product.

[0117] The yield, sepote number, inorganic content, and inorganic content of the Fischer-Tropsch wax raw material are shown in Table 2. The total content of butyl acetate and isobutyl acetate (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0118] Example 2

[0119] The method of Example 1 is different in that: in step (1), 300g of butyl acetate is replaced with an equal mass of n-butanol and heated to 110°C; in step (2), 10g of butyl acetate is replaced with 20g of n-butanol and 5g of activated clay is replaced with 10g of activated clay.

[0120] In step (5), the recovered liquid was 319g.

[0121] The yield of refined Fischer-Tropsch wax, the seppull number, the inorganic content, and the inorganic content in the Fischer-Tropsch wax raw material are shown in Table 2. The total n-butanol content (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0122] Example 3

[0123] (1) Take 100g of 90# Fischer-Tropsch wax raw material and 200g of n-butanol and mix them. Heat the mixture to 90°C until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with the n-butanol (about 15min) to obtain a completely melted wax liquid system (i.e., the first mixture).

[0124] (2) Mix 4g of activated clay, 4g of coal-based activated carbon and 16g of n-propanol, stir at 90℃ for 10min to pre-activate the activated clay and coal-based activated carbon, and obtain the adsorbent activation system (i.e. the second mixture).

[0125] (3) Mix the completely melted wax system and the adsorbent activation system, and carry out the stirring adsorption reaction for 1 hour. The stirring adsorption temperature is 90℃ to obtain a molten mixed system.

[0126] (4) The molten mixture system was filtered at 90°C to obtain refined wax liquid and filter cake containing waste adsorbent (i.e., the first filter cake);

[0127] (5) The refined wax liquid was rotary evaporated to obtain the recovered liquid (215.1g) and the refined Fischer-Tropsch wax product;

[0128] The yield of refined Fischer-Tropsch wax, the seppull number, the inorganic content, and the inorganic content in the Fischer-Tropsch wax raw material are shown in Table 2. The total content of n-butanol and n-propanol (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0129] Example 4

[0130] The method of Example 3 is different in that: in step (1), the amount of n-butanol used is 100g.

[0131] In step (5), the recovered liquid was 115.8g.

[0132] The yield of refined Fischer-Tropsch wax, the seppull number, the inorganic content, and the inorganic content in the Fischer-Tropsch wax raw material are shown in Table 2. The total content of n-butanol and n-propanol (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0133] Example 5

[0134] (1) Take 100g of 105# Fischer-Tropsch wax raw material and 300g of methyl isobutyl ketone and mix them. Heat to 105℃ until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with methyl isobutyl ketone (about 15min) to obtain a completely melted wax liquid system (i.e. the first mixture).

[0135] (2) Mix 20g of activated clay and 40g of isobutyl acetate, stir at 90℃ for 10min to pre-activate the activated clay and obtain the adsorbent activation system.

[0136] (3) Mix the completely melted wax system and the adsorbent activation system, and stir the adsorption reaction for 30 min. The stirring adsorption temperature is 110℃ to obtain a molten mixed system.

[0137] (4) The molten mixture system was filtered at 105°C to obtain refined wax liquid and filter cake containing waste activated clay (i.e. waste adsorbent) (i.e. the first filter cake).

[0138] (5) The refined wax liquid was rotary evaporated to obtain a recovery liquid (338.5g) and a refined Fischer-Tropsch wax product was obtained.

[0139] The yield, sepote number, inorganic content, and inorganic content of the Fischer-Tropsch wax product are shown in Table 2. The total content of methyl isobutyl ketone and isobutyl acetate (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0140] Example 6

[0141] The method is the same as in Example 5, except that: in step (1), the amount of methyl isobutyl ketone used is 400g. In step (2), the amount of activated clay used is 2g, and the amount of isobutyl acetate used is 4g.

[0142] In step (5), the recovered liquid is 402g.

[0143] The yield, sepote number, inorganic content, and inorganic content of the Fischer-Tropsch wax product are shown in Table 2. The total content of methyl isobutyl ketone and isobutyl acetate (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0144] Example 7

[0145] (1) Take 100g of 105# Fischer-Tropsch wax raw material and 300g of methyl isobutyl ketone and mix them. Then heat the mixture to 105℃ until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with methyl isobutyl ketone (about 15min) to obtain a completely melted wax liquid system (i.e., the first mixture).

[0146] (2) Mix 10g of adsorbent (5g of activated clay and 5g of coal-based activated carbon) and 20g of methyl isobutyl ketone, stir at 90℃ for 10min to pre-activate the activated clay and coal-based activated carbon, and obtain the adsorbent activation system (i.e. the second mixture).

[0147] (3) Mix the completely melted wax system and the adsorbent activation system, and stir the adsorption reaction for 30 min. The stirring adsorption temperature is 110℃ to obtain a molten mixed system.

[0148] (4) The molten mixture system was filtered at 105°C to obtain refined wax liquid and filter cake containing waste adsorbent (i.e., the first filter cake);

[0149] (5) The refined wax liquid was rotary evaporated to obtain a recovery liquid (318.5g) and a refined Fischer-Tropsch wax product.

[0150] The yield, seppullar special number, inorganic content, and inorganic content in the Fischer-Tropsch wax raw material are shown in Table 2. The content of methyl isobutyl ketone (i.e., additive) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0151] Example 8

[0152] In this embodiment, according to Figure 1 Perform steps (1)-(8) according to the process flow diagram shown, and follow the instructions. Figure 1 The process flow diagram shown is repeated, specifically:

[0153] (1) Take 100g of 110# Fischer-Tropsch wax raw material and 300g of butyl acetate and mix them. Heat to 120℃ until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with butyl acetate (about 15min) to obtain a completely melted wax liquid system (i.e. the first mixture).

[0154] (2) Mix 10g of activated clay and 20g of butyl acetate, stir at 110℃ for 10min to pre-activate the activated clay and obtain the adsorbent activation system (i.e., the second mixture).

[0155] (3) Mix the completely melted wax system and the adsorbent activation system, and then carry out the stirring adsorption reaction for 30 minutes at a stirring adsorption temperature of 120℃ to obtain a molten mixed system.

[0156] (4) The molten mixture system was filtered at 110°C to obtain refined wax liquid and 10.8g of filter cake containing waste activated clay (i.e. waste adsorbent) (i.e. the first filter cake);

[0157] (5) The refined wax liquid was rotary evaporated to obtain the recovery liquid (i.e. butyl acetate, 319.5g) and the refined Fischer-Tropsch wax product A1 was obtained;

[0158] (6) Take 50g of the recovered liquid obtained in step (5) and mix it with the filter cake obtained in step (4) in a beaker, stir and wash at 120℃ for 10min, and filter at 110℃ to obtain a filter cake containing regenerated activated clay (i.e., regenerated adsorbent) (i.e., the second filter cake).

[0159] (7) Mix 10.2g of filter cake containing regenerated activated clay obtained in step (6) with 20g of recovery liquid (i.e. butyl acetate) obtained in step (5), stir at 110℃ for 10min to obtain adsorbent activation system;

[0160] (8) Take 100g of 110# Fischer-Tropsch wax raw material and 300g of butyl acetate (including 249.5g of the recovery liquid obtained in step (5)) and mix them. Heat to 120°C until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with butyl acetate (about 15min) to obtain a completely melted wax liquid system. Mix the completely melted wax liquid system with the adsorbent activation system in step (7) and stir the adsorption reaction for 40min. The stirring adsorption temperature is 120°C. Then filter at 110°C to obtain refined wax liquid and 10.6g of filter cake containing waste activated clay. Vacuum distill the refined wax liquid to obtain the recovery liquid (319g) and obtain refined Fischer-Tropsch wax product A2.

[0161] (9) Take 50g of the recovered liquid obtained in step (8) and mix it with the filter cake containing waste activated clay obtained in step (8) in a beaker. Stir and wash at 120℃ for 10min, and filter at 110℃ to obtain the filter cake containing regenerated activated clay.

[0162] (10) Mix the 10.2g filter cake containing regenerated activated clay obtained in step (9) with the 20g recovery liquid (i.e. butyl acetate) obtained in step (8), and stir at 110℃ for 10min to obtain the activated clay activation system.

[0163] (11) Take 100g of 110# Fischer-Tropsch wax raw material and 300g of butyl acetate and mix them (including 249g of the recovery liquid obtained in step (8)). Heat to 120°C until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with butyl acetate (about 15min) to obtain a completely melted wax liquid system. Mix the completely melted wax liquid system with the adsorbent activation system in step (10) and stir the adsorption reaction for 40min. The stirring adsorption temperature is 120°C. Then filter at 110°C to obtain refined wax liquid and 10.7g of filter cake containing waste activated clay. Vacuum distill the refined wax liquid to obtain the recovery liquid (318.5g) and obtain refined Fischer-Tropsch wax product A3.

[0164] (12) Take 50g of the recovered liquid obtained in step (11) and mix it with the filter cake containing waste activated clay obtained in step (11) in a beaker, stir and wash at 120℃ for 10min, and filter at 110℃ to obtain the filter cake containing regenerated activated clay.

[0165] (13) Mix the 10.2g filter cake containing regenerated activated clay obtained in step (12) with 20g of the recovery liquid (i.e. butyl acetate) obtained in step (11), and stir at 110℃ for 10min to obtain the activated clay activation system.

[0166] (14) Take 100g of 110# Fischer-Tropsch wax raw material and 300g of butyl acetate and mix them (including 248.5g of the recovery liquid obtained in step (11)). Heat to 120°C until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with butyl acetate (about 15min) to obtain a completely melted wax liquid system. Mix the completely melted wax liquid system with the adsorbent activation system in step (13) and stir the adsorption reaction for 40min. The stirring adsorption temperature is 120°C. Then filter at 110°C to obtain refined wax liquid and 10.6g of filter cake containing waste activated clay. Vacuum distill the refined wax liquid to obtain recovery liquid (319g) and obtain refined Fischer-Tropsch wax product A4.

[0167] (15) Take 50g of the recovered liquid obtained in step (14) and mix it with the filter cake obtained in step (14) in a beaker, stir and wash at 120℃ for 10min, and filter at 110℃ to obtain a filter cake containing regenerated activated clay.

[0168] (16) Mix the 10.2g filter cake containing regenerated activated clay obtained in step (15) with 20g of the recovery liquid (i.e. butyl acetate) obtained in step (14), and stir at 110℃ for 10min to obtain the activated clay activation system.

[0169] (17) Take 100g of 110# Fischer-Tropsch wax raw material and 300g of butyl acetate (including 249g of the recovery liquid obtained in step (14)) and mix them. Heat to 120°C until the Fischer-Tropsch wax raw material is completely melted and mixed evenly with butyl acetate (about 15min) to obtain a completely melted wax liquid system. Mix the completely melted wax liquid system with the adsorbent activation system in step (16) and stir the adsorption reaction for 40min. The stirring adsorption temperature is 120°C. Then filter at 110°C to obtain refined wax liquid and 10.6g of filter cake containing waste activated clay. Vacuum distill the refined wax liquid to obtain the recovery liquid (318.9g) and obtain refined Fischer-Tropsch wax product A5.

[0170] The color numbers and yield results of refined Fischer-Tropsch wax products A1-A5 are shown in Table 3.

[0171] The results show that, using the method of the present invention, the adsorbent clay can be regenerated and reused at least five times, and the refined Fischer-Tropsch wax product obtained has good color and high yield.

[0172] Comparative Example 1

[0173] 100g of 100# Fischer-Tropsch wax raw material was directly mixed with 5g of activated clay and heated to 120℃ until the Fischer-Tropsch wax raw material was completely melted. The mixture was stirred and adsorbed for 30 minutes at a stirring and adsorption temperature of 120℃. The mixture was then filtered to obtain a refined wax liquid. The refined wax liquid was then subjected to rotary evaporation to obtain a refined Fischer-Tropsch wax product.

[0174] The yield of refined Fischer-Tropsch wax, the Fischer-Tropsch wax grade, the inorganic content, and the inorganic content in the Fischer-Tropsch wax raw material are shown in Table 2.

[0175] Comparative Example 2

[0176] The method is the same as in Example 1, except that the temperature for stirring and adsorption in step (3) is 150°C.

[0177] The yield, sepote number, inorganic content, and inorganic content of the Fischer-Tropsch wax raw material are shown in Table 2. The total content of butyl acetate and isobutyl acetate (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0178] Comparative Example 3

[0179] The method is the same as in Example 1, except that the stirring and adsorption time in step (3) is 120 min.

[0180] The yield, sepote number, inorganic content, and inorganic content of the Fischer-Tropsch wax raw material are shown in Table 2. The total content of butyl acetate and isobutyl acetate (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0181] Comparative Example 4

[0182] The method is the same as in Example 1, except that in step (1), butyl acetate is replaced with an equal mass of n-hexadecane.

[0183] The yield, sepote number, inorganic content, and inorganic content of the Fischer-Tropsch wax product are shown in Table 2. The total content of n-hexadecane and isobutyl acetate (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0184] Comparative Example 5

[0185] The method of Example 1 is different in that: in step (1), the amount of butyl acetate is 310g; there is no step (2); in step (3), the completely melted wax system and 5g of activated clay are directly mixed and stirred for adsorption reaction for 30min, and the stirring adsorption temperature is 120℃.

[0186] The yield, sepote number, inorganic content, and inorganic content of the Fischer-Tropsch wax raw material are shown in Table 2. The total content of butyl acetate and isobutyl acetate (i.e., additives) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0187] Comparative Example 6

[0188] Take 100g of 110# Fischer-Tropsch wax and heat it to 115℃ to completely melt the sample. Then add 10g of activated clay and stir for 30min to adsorb. Add 100g of n-butanol at 115℃ and then keep the system at 115℃ for aging for 3h. Then filter and separate at 110℃. The obtained filtrate is subjected to vacuum flash evaporation to obtain the refined Fischer-Tropsch wax product.

[0189] The yield of refined Fischer-Tropsch wax, the 'Cebo Special' grade, the inorganic content, and the inorganic content in the Fischer-Tropsch wax raw material are shown in Table 2. The content of n-butanol (i.e., aging agent) in the refined Fischer-Tropsch wax product is also shown in Table 2.

[0190] The content of aging agent (i.e. n-butanol) in the refined Fischer-Tropsch wax product was determined by the oven weight loss method: 10g of the obtained refined Fischer-Tropsch wax product was weighed, placed in an oven, the oven temperature was set 5°C higher than the boiling point of n-butanol, and dried at a constant temperature for 8 hours. The Fischer-Tropsch wax product was then taken out and weighed, and the weight was recorded as the weight of the dried refined Fischer-Tropsch wax product.

[0191] Aging agent content = (1 - weight of dried refined Fischer-Tropsch wax product / 10g of refined Fischer-Tropsch wax product) × 100%

[0192] Table 2

[0193]

[0194] Note: [1] refers to the content of inorganic matter in Fischer-Tropsch wax raw material (based on the total weight of Fischer-Tropsch wax raw material);

[0195] [2] refers to the content of inorganic matter in refined Fischer-Tropsch wax products (based on the total weight of refined Fischer-Tropsch wax products);

[0196] [3] refers to the content of additives or aging agents in refined Fischer-Tropsch wax products.

[0197] Table 3

[0198]

[0199] As can be seen from the examples, using the method of the present invention to decolorize high-melting-point Fischer-Tropsch wax can effectively improve the color number of refined Fischer-Tropsch wax products. The examples and comparative examples show that: (1) the reaction temperature and reaction time of the adsorption decolorization reaction described in the present invention can improve the decolorization effect; (2) pre-activation of the adsorbent using the method of the present invention can improve the decolorization effect; (3) the adsorption decolorization effect is better when polar organic solvents are used as auxiliaries than when non-polar solvents are used as auxiliaries; (4) existing Fischer-Tropsch wax decolorization methods are not suitable for high-melting-point Fischer-Tropsch wax, and the method of the present invention can achieve a better decolorization effect.

[0200] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A process for improving the color of high melting point Fischer-Tropsch waxes characterized by, The method comprises: (1) mixing a material containing a first additive with a Fischer-Tropsch wax raw material to obtain a first mixture; the first mixture is a completely melted wax liquid system; (2) mixing an activator containing a second additive with a decolorizing agent containing an adsorbent to obtain a second mixture; the adsorbent is activated clay and / or activated carbon; the second mixing condition is that the temperature is 90-110°C and the time is 5-30 min; (3) mixing the first mixture and the second mixture to perform adsorption to obtain a molten mixed system; (4) performing first solid-liquid separation on the molten mixed system to obtain a first filter cake and a refined wax liquid; (5) distilling the refined wax liquid to obtain a recovery liquid and a refined Fischer-Tropsch wax product; In step (3), the adsorption condition is that the temperature is 90-130°C and the time is 30-60 min. The first additive and the second additive are independently selected from at least one of alcohol organic matter, ester organic matter and ketone organic matter.

2. The method of claim 1, wherein, The method further comprises: adding a first part of the recovery liquid obtained in step (5) to the material in step (1), adding a second part to the activator in step (2), and adding a third part to wash the first filter cake obtained in step (4); after the washing, second solid-liquid separation is performed to obtain a second filter cake.

3. The method of claim 2, wherein, The second filter cake is added to the decolorizing agent in step (2).

4. The method of claim 2, wherein, The washing temperature is 90-120°C and the washing time is 10-20 min.

5. The method of any of claims 1-4, wherein, The melting point of the Fischer-Tropsch wax raw material is ≥80°C; And / or, the Saybolt color number of the Fischer-Tropsch wax raw material is ≤-16.

6. The method of claim 1, wherein, The alcohol organic matter is at least one of n-propanol, n-butanol, isobutyl alcohol, 1-pentanol, isopentyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, sec-octanol and isooctyl alcohol; And / or, the ester organic matter is at least one of ethyl acetate, ethyl propionate, ethyl butyrate, n-propyl acetate, isopropyl acetate, isobutyl acetate and isooctyl acetate; And / or, the ketone organic matter is at least one of butanone, 2-pentanone, 3-pentanone, 3,3-dimethyl-2-butanone, diethyl ketone, 3-methyl-2-pentanone, methyl isobutyl ketone, methyl sec-butyl ketone, cyclobutanone, benzophenone and isophorone.

7. The method of any one of claims 1-4, wherein, The first mixing condition is that the temperature is 90-120°C and the time is 15-30 min; And / or, the first solid-liquid separation temperature is 90-130°C.

8. The method of any one of claims 1-4, wherein, The mass ratio of the Fischer-Tropsch wax raw material to the material is 1:1-4; And / or, the mass ratio of the decolorizing agent to the activator is 1:1-2; And / or, the amount of the decolorizing agent is 2-20 parts by weight relative to 100 parts by weight of the Fischer-Tropsch wax raw material.

9. The method of any one of claims 1-4, wherein, The Saybolt color number of the refined Fischer-Tropsch wax product is ≥+13.

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