A catalyst based on biomass cashew nut shell oil, and a preparation method and application thereof

Abstract

The application provides a catalyst based on biomass cashew nut shell oil and a preparation method and application thereof, and relates to the technical field of hydrogenation catalysts. The preparation method of the catalyst based on biomass cashew nut shell oil comprises the following steps: dissolving cold-pressed cashew nut shell oil in a solvent, adding a sodium hydroxide solution, mixing, heating and reacting until the pH is 8.1-8.25, then obtaining a saponification solution containing sodium cashewate through sedimentation; adding a nickel nitrate hexahydrate solution and n-hexane to the saponification solution, heating, stirring and reacting to obtain a precursor solution containing nickel cashewate; adding a solvent to the precursor solution for dilution, and then performing water washing, dehydration and desolventizing treatment, and finally drying to obtain the catalyst product. The cold-pressed cashew nut shell oil containing cashew acid is used as a raw material, saponification reaction and double decomposition reaction are performed, nickel cashewate is prepared, the preparation method is simple and convenient, and the content and recovery rate of the nickel cashewate can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogenation catalyst, in particular to a catalyst based on biomass cashew nut shell oil and a preparation method and application thereof. BACKGROUND

[0002] With the increasing scarcity of world oil resources, coal oil co-refining hydrocarbon industry has been widely concerned. Coal direct liquefaction catalysts can be divided into three categories, the first category is cobalt, molybdenum, nickel and other metal catalysts; the second category is metal halide catalysts, such as ZnCl2 and SnCl2; the third category is iron-based disposable catalysts, such as iron-containing natural minerals, industrial waste residues and synthetic iron-containing compounds. Studies have shown that the first category of catalysts has high activity and is widely used in the field of petroleum hydrofining. However, this type of catalyst is expensive, and from an economic point of view, it needs to be regenerated repeatedly, and the coal direct liquefaction system is difficult to realize the recovery and regeneration of the catalyst, so this type of catalyst is difficult to be applied to coal direct hydrogenation liquefaction. SUMMARY

[0003] The purpose of the present application is to provide a catalyst based on biomass cashew nut shell oil, which has the advantages of good catalytic effect and can be used as a hydrogenation catalyst in the field of coal / heavy oil hydrogenation liquefaction.

[0004] Another purpose of the present application is to provide a preparation method of a catalyst based on biomass cashew nut shell oil, which can improve the recovery rate of nickel.

[0005] Another purpose of the present application is to provide a catalyst based on biomass cashew nut shell oil in the field of coal / heavy oil hydrogenation liquefaction as a hydrogenation catalyst.

[0006] To solve the above technical problems, the technical scheme adopted by the present application is:

[0007] On the one hand, the present application provides a preparation method of a catalyst based on biomass cashew nut shell oil, comprising the following steps:

[0008] Saponification reaction: dissolve cold-pressed cashew nut shell oil in a solvent, add sodium hydroxide solution and mix, heat to react to pH 8.1-8.25, then obtain a saponification solution containing sodium cashewate after settling;

[0009] Double decomposition reaction: add nickel nitrate hexahydrate solution and n-hexane to the saponification solution, heat and stir to react, to obtain a precursor solution containing nickel cashewate;

[0010] Post-processing: the precursor solution is diluted by adding solvent, and then treated by water washing, dehydration and desolventization, and dried to obtain the catalyst product.

[0011] In another aspect, the application provides a catalyst based on biomass cashew nut shell oil, which is prepared by the above preparation method.

[0012] In another aspect, the application provides the application of a catalyst based on biomass cashew nut shell oil as a hydrogenation catalyst in the field of coal / heavy oil hydroliquefaction.

[0013] Compared with the prior art, the embodiments of the application have at least the following advantages or beneficial effects:

[0014] 1. The application uses cold-pressed cashew nut shell oil as raw material, which mainly contains anacardic acid. The anacardic acid nickel is prepared by saponification reaction and metathesis reaction. The preparation method is simple and convenient, which can improve the content and recovery rate of anacardic acid nickel. The raw material cashew nut shell oil in the application is obtained by cold-pressing treatment from discarded cashew nut shells, which is low in price, high in yield in tropical countries near the equator, and large in import quantity in coastal areas of China. It does not need to be artificially synthesized, and is low in cost and more environmentally friendly, and is more suitable for wide application.

[0015] 2. The anacardic acid nickel prepared in the application is applied as a hydrogenation catalyst in the field of coal / heavy oil hydroliquefaction, which has high catalytic efficiency and does not produce additional pollution.

[0016] 3. The process of the application is also applicable to the preparation of other fatty acid nickel with benzene ring and carbon long branch chain. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0018] Figure 1 TG and DTG curves of anacardic acid nickel in Example 1 of the application;

[0019] Figure 2 Infrared spectrum of anacardic acid in cold-pressed cashew nut shell oil in Example 1 of the application;

[0020] Figure 3 Infrared spectrum of anacardic acid nickel obtained by metathesis reaction in Example 1 of the application;

[0021] Figure 4 Pressure curve of catalytic hydrogenation reaction in Example 1 of the application;

[0022] Figure 5 This is a microscopic image of the oil-coal slurry after the reaction using nickel naphthenate as a catalyst precursor in Experimental Example 1 of this application.

[0023] Figure 6 This is a microscopic image of the oil-coal slurry after the reaction using nickel cashew tar as a catalyst precursor in Experiment Example 1 of this application. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0025] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present application will now be described in detail with reference to specific embodiments.

[0026] A method for preparing a catalyst based on biomass cashew nut shell oil includes the following steps:

[0027] Saponification reaction: Cold-pressed cashew shell oil is dissolved in a solvent and mixed with sodium hydroxide solution. The mixture is heated to a pH of 8.1-8.25 and then settled to obtain a saponified solution containing sodium cashew nutate.

[0028] Metathesis reaction: Add nickel nitrate hexahydrate solution to the saponification solution, add n-hexane, heat and stir to react, and obtain a precursor solution containing nickel cashew nutate;

[0029] Post-processing: The precursor solution is diluted with solvent, and then washed with water, dehydrated and desolventized, and then dried to obtain the catalyst product.

[0030] In some embodiments of this application, the molar ratio of cold-pressed cashew nut shell oil to sodium hydroxide in the above saponification reaction step is 1:(0.95-1.05).

[0031] In some embodiments of this application, the solvent in the above saponification reaction step is ethanol, and the concentration of the sodium hydroxide solution is 10-15%.

[0032] In some embodiments of this application, the heating temperature in the above saponification reaction step is 90-100°C, the reaction time is 2-4 hours, and the sedimentation time is 20-40 minutes.

[0033] In some embodiments of this application, the molar ratio of nickel nitrate hexahydrate to sodium cashew precipitate in the saponification solution in the above metathesis reaction step is (0.95-1.02):1.

[0034] In some embodiments of the present application, the heating temperature in the above metathesis reaction step is 90-100℃, the dropping time of the nickel nitrate hexahydrate solution is 1-1.5h, and the reaction is continued for 2-3h after the dropping is completed.

[0035] In some embodiments of the present application, the solvent in the above post-treatment step is toluene or xylene, the water washing is 2-3 times, the drying temperature is 105-115℃, and the drying time is 2-4h.

[0036] A biomass cashew nut shell oil-based catalyst prepared by the above preparation method.

[0037] Application of a biomass cashew nut shell oil-based catalyst as a hydrogenation catalyst in the field of coal / heavy oil hydroliquefaction.

[0038] The features and performances of the present application are further described in detail below in combination with examples.

[0039] Example 1

[0040] A biomass cashew nut shell-based hydrogenation catalyst is prepared by the following method:

[0041] Saponification reaction: cold-pressed cashew nut shell oil is dissolved in 20mL of an ethanol solution, then 12% sodium hydroxide aqueous solution is added to a three-necked flask in a molar ratio of 1:0.99, a stirrer is started, and the temperature is raised to 95℃, and the reaction time is 3h. The pH value is tested by a pH meter, and the reaction is terminated when the pH value reaches 8.1. The separation of the oil phase and the soap phase after the saponification reaction is achieved by natural sedimentation, and the saponified solution containing sodium cashewate is separated after the saponification solution is left to stand for about 30min.

[0042] Metathesis reaction: the molar ratio of sodium cashewate to Ni(NO3)2·6H2O is 2:0.98, 40mL of an aqueous solution of Ni(NO3)2·6H2O is added dropwise to the saponified solution, 5mL of n-hexane is added, a stirrer is started, the temperature is maintained at 95℃, the dropping time is 1.0 (4-5 seconds for one drop), and the reaction is continued for 3h after the dropping is completed to obtain a precursor solution containing nickel cashewate.

[0043] Post-treatment process: nickel cashewate is prepared in the second step, but the product contains a large amount of inorganic salts (mainly NaNO3), which need to be removed by water washing. However, the viscosity of naphthenate is large, so a certain amount of solvent (toluene) needs to be added for dilution to facilitate the water washing and maintain a certain temperature. The water washing is 2 times, and after the water washing is completed and the water layer is discharged, dehydration and desolventization treatment are carried out. The dehydration drying temperature is controlled at 110℃, and the drying time is 3h.

[0044] The TG and DTG curves of the nickel cashewate prepared in this example are shown in Figure 1 The TG and DTG curves of the nickel cashewate prepared in this example are shown inFigure 1 The thermogravimetric curves show that the nickel cashew nut shell oil prepared in this embodiment is easily decomposed at high temperatures, which is beneficial for nickel to fully exert its catalytic effect in the kerosene co-refining hydrogenation system. The infrared spectra of cashew acid in cold-pressed cashew shell oil and nickel cashew nut shell oil obtained from the metathesis reaction are shown below. Figure 2 and Figure 3 As shown.

[0045] Example 2

[0046] A hydrogenation catalyst based on biomass cashew nut shells is prepared as follows:

[0047] Saponification reaction: Cold-pressed cashew nut shell oil was dissolved in 20 mL of ethanol solution, and then added to a three-necked flask with 15% sodium hydroxide aqueous solution at a molar ratio of 1:1. The mixture was stirred and heated to 100°C for 2 hours. The reaction was terminated when the pH reached 8.15. The separation of the oil phase and soap phase after saponification was achieved through natural sedimentation. After saponification, the mixture was allowed to stand for approximately 30 minutes to separate and obtain a saponified solution containing sodium cashew nutate.

[0048] Double decomposition reaction: The molar ratio of sodium cashew tartaric acid to Ni(NO3)2·6H2O is 2:0.99. 40 mL of Ni(NO3)2·6H2O aqueous solution is added dropwise to the saponification solution, and 5 mL of n-hexane is added. The stirrer is turned on and the temperature is maintained at 95℃. The dropping time is 1.0 (1 drop every 4-5 seconds). After the dropping is completed, the reaction continues for 2 hours to obtain a precursor solution containing nickel cashew tartaric acid.

[0049] Post-processing: Nickel cashew nutate was produced in the second step, but it contains a relatively high amount of inorganic salts (mainly NaNO3), which need to be removed by washing with water. However, naphthenates have a high viscosity, so to facilitate water washing and separation, a certain temperature was maintained, and a certain amount of solvent (toluene) was added for dilution. The product was washed twice, and after the water layer was drained, it underwent dehydration and solvent removal. The dehydration and drying temperature was controlled at 110℃ for 2 hours.

[0050] Example 3

[0051] A hydrogenation catalyst based on biomass cashew nut shells is prepared as follows:

[0052] Saponification reaction: Cold-pressed cashew nut shell oil was dissolved in 20 mL of ethanol solution, and then added to a three-necked flask with 10% sodium hydroxide aqueous solution at a molar ratio of 1:0.99. The stirrer was turned on, and the temperature was raised to 92°C for 3 hours. The reaction was terminated when the pH value reached 8.1. The separation of the oil phase and soap phase after saponification was achieved by natural sedimentation. After saponification, the mixture should be allowed to stand for about 30 minutes to separate and obtain a saponified solution containing sodium cashew nutate.

[0053] Double decomposition reaction: the molar ratio of sodium cashewate: Ni(NO3)2.6H2O = 2: 1.01, 40 mL of Ni(NO3)2.6H2O aqueous solution was added dropwise into the saponification solution, 5 mL of n-hexane was added, and the stirrer was started, the temperature was maintained at 95℃, the dropwise time was 1.5 (4-5 seconds per drop), after the dropwise addition was completed, the reaction was continued for 3 h, and a precursor solution containing nickel cashewate was obtained.

[0054] Post-processing process: nickel cashewate was prepared by the second step, but the material contains a large amount of inorganic salt (mainly NaNO3), which needs to be removed by water washing. However, the viscosity of naphthenate is large, in order to make the water washing layering convenient, a certain temperature is maintained, and a certain amount of solvent (toluene) needs to be added for dilution. Water washing 3 times, after the water washing is completed and the water layer is discharged, dehydration and desolventizing treatment is carried out. The dehydration drying control temperature is 112℃, and the drying time is 4 h.

[0055] Example 4

[0056] A biomass cashew nut shell based hydrogenation catalyst is prepared by the following method:

[0057] Saponification reaction: cold-pressed cashew nut shell oil was dissolved in 20 mL of ethanol solution, then 12% sodium hydroxide aqueous solution was added into a three-necked flask according to the molar ratio of 1:0.99, the stirrer was started, the temperature was heated to 92℃, and the reaction time was 2 h. The pH value was tested by pH meter to reach 8.25, and the reaction experiment was terminated. The separation of oil phase and soap phase after saponification reaction was realized by natural sedimentation, and the saponification solution containing sodium cashewate was separated after saponification for about 30 min.

[0058] Double decomposition reaction: the molar ratio of sodium cashewate: Ni(NO3)2.6H2O = 2: 0.99, 40 mL of Ni(NO3)2.6H2O aqueous solution was added dropwise into the saponification solution, 5 mL of n-hexane was added, and the stirrer was started, the temperature was maintained at 95℃, the dropwise time was 1.5 (4-5 seconds per drop), after the dropwise addition was completed, the reaction was continued for 2.5 h, and a precursor solution containing nickel cashewate was obtained.

[0059] Post-processing process: nickel cashewate was prepared by the second step, but the material contains a large amount of inorganic salt (mainly NaNO3), which needs to be removed by water washing. However, the viscosity of naphthenate is large, in order to make the water washing layering convenient, a certain temperature is maintained, and a certain amount of solvent (toluene) needs to be added for dilution. Water washing 3 times, after the water washing is completed and the water layer is discharged, dehydration and desolventizing treatment is carried out. The dehydration drying control temperature is 115℃, and the drying time is 1 h.

[0060] Example 5

[0061] A biomass cashew nut shell based hydrogenation catalyst is prepared by the following method:

[0062] Saponification reaction: The cold-pressed cashew nut shell oil was dissolved in 20 mL of ethanol solution, then added to a three-necked flask with 12% sodium hydroxide aqueous solution at a molar ratio of 1:0.99, the stirrer was started, and the temperature was heated to 92°C, and the reaction time was 2 h. The pH value was tested by a pH meter to reach 8.25, and the reaction was terminated. The separation of the oil phase and the soap phase after saponification was achieved by natural sedimentation, and the saponified solution containing sodium cashewate was separated after standing for about 30 min.

[0063] Double decomposition reaction: The molar ratio of sodium cashewate: Ni(NO3)2·6H2O was 2:0.99, and 40 mL of Ni(NO3)2·6H2O aqueous solution was added dropwise to the saponified solution, 5 mL of n-hexane was added, and the stirrer was started. The temperature was maintained at 90°C, the dropwise time was 1.5 h (4-5 seconds per drop), and the dropwise addition was completed. After 3 h of continuous reaction, a precursor solution containing nickel cashewate was obtained.

[0064] Post-treatment process: Nickel cashewate was prepared in the second step, but it contained a lot of inorganic salts (mainly NaNO3), which needed to be removed by water washing. However, the viscosity of naphthenate salt was large, so a certain amount of solvent (toluene) was added for dilution to facilitate the water washing and maintain a certain temperature. Water washing was performed 3 times, and after the water washing was completed and the water layer was discharged, dehydration and desolventization treatment were performed. The dehydration drying control temperature was 105°C, and the drying time was 2 h.

[0065] Experimental example

[0066] (1) Application of catalyst

[0067] In this experimental example, the catalyst product prepared in Example 1 was used as a hydrogenation catalyst for coal / heavy oil hydroliquefaction. Since the aromatic content in the Marusia residue (MRAR) is low and the C7-asphaltene content is high, and the aromatic content in the catalytic cracking slurry (FCCS) is high and the C7-asphaltene content is low, in order to investigate the catalytic hydrogenation performance of the catalyst in different reaction materials and avoid the contingency caused by a single raw material, two types of reaction materials were selected for testing.

[0068] 1. Marusia residue experimental conditions:

[0069] Experimental materials: Marusia residue, Xinjiang lignite (42% coal mass content in oil slurry), 1000 μg / g of catalyst precursor (calculated based on Ni content), and 2000 μg / g of sulfur powder.

[0070] Experimental conditions: 500 mL high-pressure reaction kettle, hydrogen pressure 8.0 MPa, rotation speed 250 r / min, reaction temperature 420°C, reaction time 60 min.

[0071] Product post-processing: collect the gaseous product (to be tested), take part of the liquid-solid product for atmospheric and vacuum distillation and calculate the yield of each fraction, and another part for toluene filtration extraction and calculate the solid residue rate. Compared with the control group without catalyst, the change of the hydrogenation co-treatment pressure is as shown in Figure 4 Figure 4 It can be seen from

[0072] The experiment also sets a control group: using naphthenic acid nickel as catalyst precursor for coal / heavy oil hydrocracking reaction;

[0073] The microscope images of the oil coal slurry after the reaction of naphthenic acid nickel and cashew acid nickel as catalyst precursor are shown in Figure 5 Figure 6 It can be seen from Figure 5 Figure 6 and

[0074] 2. Catalytic cracking slurry experiment conditions:

[0075] Experimental raw materials: catalytic cracking slurry, Xinjiang lignite (42% coal content in oil coal slurry), other experimental conditions are the same as those of Ma Sai residual oil, and the experimental results are basically the same as those of Ma Sai residual oil.

[0076] (II) Explore the effect of different double decomposition reaction times on the yield of catalyst precursor.

[0077] The present application sets up 4 experimental groups, the only difference is that the reaction time of double decomposition is different (2h, 3h, 4h, 5h respectively), and the yield of the precursor is calculated, as shown in Table 1. The yield of the remaining fatty acid nickel (nickel octanoate, nickel dodecanoate, nickel tetradecanoate, nickel hexadecanoate, nickel oleate, nickel naphthenate) precursor at different double decomposition times is also shown in Table 1:

[0078]

[0079] Table 1

[0080]

[0081]

[0082] ​​​As can be seen from Table 1, the content of cashew nut acid nickel and other various nickel fatty acids all show a trend of first increasing and then decreasing within 2-5h of the metathesis reaction, and reach the peak at 3h, which indicates that the suitable time of the metathesis reaction is 2-3h, especially 3h is the best.

[0083] In summary, the catalyst based on biomass cashew nut shell oil, its preparation method and application have the following advantages:

[0084] 1. The cold-pressed cashew nut shell oil is used as the raw material in the present application, and the main component is cashew acid, which is prepared into cashew nut acid nickel through saponification reaction and metathesis reaction. The preparation method is simple and convenient, can improve the content and recovery rate of cashew nut acid nickel, and the raw material cashew nut shell oil of the present application is obtained from discarded cashew nut shells after cold-pressing treatment, which is low in price, high in yield in the equatorial tropical countries, large in import quantity in the coastal areas of China, does not need to be artificially synthesized, is low in cost and more environmentally friendly, and is more suitable for wide application.

[0085] 2. The prepared cashew nut acid nickel is applied as a hydrogenation catalyst in the field of coal / heavy oil hydrocracking, which has high catalytic efficiency and does not produce additional pollution.

[0086] 3. The process of the present application is also suitable for the preparation of other nickel fatty acids with benzene rings and carbon long branched chains.

[0087] The above-described embodiments are part of the embodiments of the present application, rather than all the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but only represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

Claims

1. Use of a catalyst based on biomass cashew nut shell oil in the field of coal / heavy oil hydro- liquefaction as a hydrogenation catalyst, characterized in that, The preparation method of the catalyst comprises the following steps: The saponification reaction: the cold-pressed cashew shell oil is dissolved in a solvent, and a sodium hydroxide solution is added for mixing and heating reaction until the pH is 8.1-8.25, and then the saponification solution containing sodium cashewate is obtained after sedimentation; The metathesis reaction: the saponification solution is added with a nickel nitrate hexahydrate solution and n-hexane, and heated and stirred to obtain a precursor solution containing nickel cashewate; The post-treatment: the precursor solution is diluted by adding a solvent, and then treated by water washing, dehydration and desolvation, and dried to obtain the catalyst product; wherein the solvent is toluene or xylene, the water washing is 2-3 times, the drying temperature is 105-115 DEG C, and the drying time is 2-4 h.

2. Use of a catalyst based on biomass cashew nut shell oil according to claim 1 in the field of coal / heavy oil hydroliquefaction as a hydrogenation catalyst, characterized in that, The molar ratio of the cold-pressed cashew shell oil to sodium hydroxide in the saponification reaction step is 1: (0.95-1.05).

3. Use of a catalyst based on biomass cashew nut shell oil according to claim 2 in the field of coal / heavy oil hydroliquefaction as a hydrogenation catalyst, characterized in that, The solvent in the saponification reaction step is ethanol, and the concentration of the sodium hydroxide solution is 10-15%.

4. Use of a catalyst based on biomass cashew nut shell oil according to claim 1 in the field of coal / heavy oil hydroliquefaction as a hydrogenation catalyst, characterized in that, The heating temperature in the saponification reaction step is 90-100 DEG C, the reaction time is 2-4 h, and the sedimentation time is 20-40 min.

5. Use of a catalyst based on biomass cashew nut shell oil according to claim 1 in the field of coal / heavy oil hydroliquefaction as a hydrogenation catalyst, characterized in that, The molar ratio of the nickel nitrate hexahydrate to sodium cashewate in the saponification solution in the metathesis reaction step is (0.95-1.02):

1.

6. Use of a catalyst based on biomass cashew nut shell oil according to claim 1 in the field of coal / heavy oil hydroliquefaction as a hydrogenation catalyst, characterized in that, The heating temperature in the metathesis reaction step is 90-100 DEG C, the dropping time of the nickel nitrate hexahydrate solution is 1-1.5 h, and the reaction time after dropping is 1-4 h.

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