A slurry oil settling agent, its preparation method and application

Abstract

The present application relates to a kind of oil slurry settling agent and its preparation method and application, belong to oil additive technical field.The oil slurry settling agent provided by the present application includes the following raw materials by mass fraction: polyether mixture 25~40 parts, solubilizing agent 10~15 parts, dispersing agent 10~15 parts, solvent 35~50 parts;Wherein, the polyether mixture includes the following mass percentage components: tallow amine polyoxyethylene ether 25%~35%, polyoxyethylene laurate 25%~35%, alkyl phenol polyoxyethylene polyoxypropylene ether 30%~50%.The oil slurry settling agent of the present application can accelerate the separation of catalytic cracking oil slurry and the catalyst powder therein, reduce the ash content in catalytic cracking oil slurry to within 500ppm, improve the added value of oil slurry, and provide important quality assurance for subsequent processing.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of oil additives, and particularly relates to an oil slurry settling agent and a preparation method and application thereof. BACKGROUND

[0002] Catalytic cracking (FCC) slurry is the main heavy oil separated from catalytic cracking unit with a boiling point > 340℃, and its main component is condensed ring aromatic hydrocarbon, which can be used as a raw material for various chemical products and has good economic benefits. In recent years, however, due to the deterioration of crude oil itself and the increase of the ratio of vacuum residue, the ash content of catalytic cracking slurry becomes higher and higher (generally 0.1wt%~2wt%), which greatly limits the use of catalytic cracking slurry.

[0003] At present, catalytic cracking slurry has the following applications: (1) Catalytic cracking slurry is used for producing carbon black, and the ash content in the slurry should be below 0.05wt% when used for this purpose. (2) Catalytic cracking slurry is used for blending fuel oil, but if the catalyst powder in the slurry is not removed, the catalyst powder in the slurry will increase the wear degree of the fire nozzle of the heating furnace, cause the ash deposition on the surface of the heating furnace, increase the energy consumption, and reduce the thermal efficiency. (3) Catalytic cracking slurry is used as a raw material for producing needle coke, which can be used as a primary product for preparing graphite electrodes. Since the ash will leave voids in the needle coke during the preparation of graphite, the ash content in the slurry must also be below 0.05wt%. (4) Catalytic cracking slurry is used as a raw material for hydrocracking, but the catalyst powder contained in the slurry will block the pores of the catalyst and deactivate the catalyst. Therefore, it is necessary to reduce the ash content of catalytic cracking slurry.

[0004] In the prior art, the methods for removing the ash in catalytic cracking slurry mainly include filtration, electrostatic separation, centrifugal separation, natural sedimentation, and additive settling method. The filtration method separates the catalyst powder in the catalytic cracking slurry through a specially designed filter. This method has strict requirements for the pore size and material of the filter, is complicated to operate, the filter pores are easy to be blocked, and the maintenance cost is high. The electrostatic separation method is generally used for the slurry with low ash content and small catalyst particle size, and the smaller the particle size of the catalyst, the easier it is to be adsorbed. Although this method has high processing efficiency, it has high equipment cost and operating cost, and is selective to the properties of the slurry. The centrifugal separation method is relatively complex to operate and maintain, and has small single processing capacity, which is difficult to realize industrialization. The natural sedimentation method only uses the gravity sedimentation of the catalyst powder, has low efficiency, long sedimentation period, and the ash content in the final slurry is relatively high. This method is only suitable for a small amount of slurry. The additive settling method has the advantages of low additive cost, low requirement for equipment, and easy realization, and is a promising method for removing the ash in the slurry.

[0005] However, the auxiliary agent settling method is an economical and effective oil slurry ash settling method, but the oil slurry settling agent on the market has the problems of poor use effect and poor adaptability, which limits the popularization and use of the method, therefore, it has great practical significance to develop a high-efficiency and universal oil slurry settling agent. SUMMARY

[0006] The present application aims to overcome the problems in the prior art, and provides an oil slurry settling agent, a preparation method and application thereof.

[0007] The present application is achieved by the following technical solutions:

[0008] The present application provides an oil slurry settling agent, which comprises the following raw materials in parts by mass: 25-40 parts of a polyether mixture, 10-15 parts of a solubilizing agent, 10-15 parts of a dispersing agent, and 35-50 parts of a solvent; wherein the polyether mixture comprises the following components in mass percentage: 25-35% of a tallow amine polyoxyethylene ether, 25-35% of a polyoxyethylene laurate, and 30-50% of an alkylphenol polyoxyethylene polyoxypropylene ether.

[0009] The oil slurry settling agent provided by the present application can eliminate the electrostatic repulsion between the surface charges of the catalyst powder particles in the oil slurry, weaken the polarity between the catalyst powder particles, and destroy the stability of the oil slurry system, so that the catalyst particles in the oil slurry can be quickly settled; the polyether mixture is used in combination with the solubilizing agent, the dispersing agent, and the solvent, which can avoid the problems of stratification and uneven mixing of the oil slurry settling agent, and make the oil slurry settling agent uniformly dispersed in the oil slurry with high settling efficiency. The oil slurry settling agent provided by the present application can reduce the ash content of the catalytic cracking oil slurry (original ash content of 0.1wt%-2wt%) to below 0.05wt% within 24 hours.

[0010] As a preferred embodiment of the oil slurry settling agent of the present application, the tallow amine polyoxyethylene ether has a hydrophilic-lipophilic balance (HLB) value of 2-10 and an average molecular weight of 2000-8000.

[0011] Preferably, the tallow amine polyoxyethylene ether has an HLB value of 2-5 and an average molecular weight of 3000-5000.

[0012] As a preferred embodiment of the oil slurry settling agent of the present application, the polyoxyethylene laurate has an HLB value of 2-15 and an average molecular weight of 300-1200.

[0013] Preferably, the polyoxyethylene laurate has an HLB value of 2-8 and an average molecular weight of 400-800.

[0014] As a preferred embodiment of the oil slurry settling agent of the present application, the HLB value of the alkyl phenol polyoxyethylene polyoxypropylene ether is 2-15, and the average molecular weight is 1000-6000.

[0015] Preferably, the HLB value of the alkyl phenol polyoxyethylene polyoxypropylene ether is 4-7, and the average molecular weight is 2000-4000.

[0016] As a preferred embodiment of the oil slurry settling agent of the present application, the solubilizing agent is polypropylene glycol, and the average molecular weight of the polypropylene glycol is 1000-4000.

[0017] Preferably, the average molecular weight of the polypropylene glycol is 1500-2500.

[0018] As a preferred embodiment of the oil slurry settling agent of the present application, the dispersing agent is oil-soluble phenolic resin, and the average molecular weight of the oil-soluble phenolic resin is 2000-5000.

[0019] Preferably, the average molecular weight of the oil-soluble phenolic resin is 2500-3500, and the oil-soluble phenolic resin is t-butyl phenol formaldehyde resin and / or nonyl phenol formaldehyde resin.

[0020] As a preferred embodiment of the oil slurry settling agent of the present application, the solvent is high flash point solvent, and the high flash point solvent is 150# aromatic hydrocarbon solvent oil and / or 1800# aromatic hydrocarbon solvent oil.

[0021] The high flash point solvent of the present application is a kind of high flash point solvent well known to those skilled in the art.

[0022] Still another object of the present application is to provide a preparation method of the above-mentioned oil slurry settling agent, comprising the following steps: mixing the polyether mixture, the solubilizing agent, the dispersing agent, and the solvent, and stirring uniformly to obtain.

[0023] In the preparation method of the present application, the mixing operation and conditions are conventional operation conditions in the art, i.e., can be carried out at normal pressure and room temperature, and the conventional normal pressure well known to those skilled in the art is 20℃ and 1 standard atmosphere.

[0024] Still another object of the present application is to provide the application of the above-mentioned oil slurry settling agent and the preparation method thereof in oil slurry ash settling.

[0025] As a preferred embodiment of the application of the present application, 100ppm-1000ppm of the oil slurry settling agent is uniformly mixed with oil slurry to obtain.

[0026] Preferably, the oil slurry settling agent of the present application is applied to accelerate the settling and removal of catalyst powder in catalytic cracking oil slurry.

[0027] The oil slurry settling agent of the present application is a colorless to light yellow liquid oil-soluble product with a density of 0.80-1.0 g / cm 3 (GB / T 1884); flash point > 60℃ (GB / T 261); solidification point < -20℃ (GB / T 510).

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] 1. The oil slurry settling agent of the present application can quickly remove ash in the oil slurry, and can reduce the ash content of catalytic cracking oil slurry (original ash content of 0.1wt%-2wt%) to below 0.05wt% within 24h.

[0030] 2. The oil slurry settling agent of the present application has small dosage and low ash content after oil slurry settling, and can be applied to most oil slurry of refineries.

[0031] 3. The oil slurry settling agent of the present application has simple production process flow, simple operation, low equipment requirement and low running cost. DETAILED DESCRIPTION

[0032] To better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in combination with specific examples. Those skilled in the art should understand that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0033] The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents, etc. used are all commercially available unless otherwise specified. The grade of polypropylene glycol (1500) described in Table 1 is PPG-1500, which is purchased from Jiangsu Hai'an Petrochemical Factory;

[0034] The grade of polypropylene glycol (2500) is PPG-2500, which is purchased from Jiangsu Hai'an Petrochemical Factory;

[0035] The oil-soluble phenolic resin is purchased from Hubei Kovol Chemical Co., Ltd.;

[0036] The grade of 1800# aromatic hydrocarbon solvent oil is S-1800#, which is purchased from Nantong Runfeng Petrochemical Co., Ltd.;

[0037] The grade of 150# aromatic hydrocarbon solvent oil is S-150#, which is purchased from Nantong Runfeng Petrochemical Co., Ltd.

[0038] The raw material ratio of the oil slurry settling agent of Examples 1-4 and Comparative Examples 1-7 of the present application is shown in Table 1:

[0039] Table 1 Raw material ratio of the oil slurry settling agent of Examples 1-4 and Comparative Examples 1-7 (mass percent)

[0040]

[0041]

[0042] The polyether mixture A in Table 1 is formulated to include, by mass percentage, 25% of a polyoxyethylene lauric acid ester, 25% of an alkylphenol polyoxyethylene polyoxypropylene ether, and 50% of a polyoxyethylene lauryl amine; the polyoxyethylene lauric acid ester has an HLB value of 2 and an average molecular weight of 400; the alkylphenol polyoxyethylene polyoxypropylene ether has an HLB value of 4 and an average molecular weight of 2000; and the polyoxyethylene lauryl amine has an HLB value of 2 and an average molecular weight of 3000.

[0043] The polyether mixture B in Table 1 is formulated to include, by mass percentage, 35% of a polyoxyethylene lauric acid ester, 35% of an alkylphenol polyoxyethylene polyoxypropylene ether, and 30% of a polyoxyethylene lauryl amine; the polyoxyethylene lauric acid ester has an HLB value of 2 and an average molecular weight of 400; the alkylphenol polyoxyethylene polyoxypropylene ether has an HLB value of 4 and an average molecular weight of 2000; and the polyoxyethylene lauryl amine has an HLB value of 2 and an average molecular weight of 3000.

[0044] The polyether mixture C in Table 1 is formulated to include, by mass percentage, 25% of a polyoxyethylene lauric acid ester, 25% of an alkylphenol polyoxyethylene polyoxypropylene ether, and 50% of a polyoxyethylene lauryl amine; the polyoxyethylene lauric acid ester has an HLB value of 8 and an average molecular weight of 800; the alkylphenol polyoxyethylene polyoxypropylene ether has an HLB value of 7 and an average molecular weight of 4000; and the polyoxyethylene lauryl amine has an HLB value of 5 and an average molecular weight of 5000.

[0045] The polyether mixture D in Table 1 is formulated to include, by mass percentage, 35% of a polyoxyethylene lauric acid ester, 35% of an alkylphenol polyoxyethylene polyoxypropylene ether, and 30% of a polyoxyethylene lauryl amine; the polyoxyethylene lauric acid ester has an HLB value of 8 and an average molecular weight of 800; the alkylphenol polyoxyethylene polyoxypropylene ether has an HLB value of 7 and an average molecular weight of 4000; and the polyoxyethylene lauryl amine has an HLB value of 5 and an average molecular weight of 5000.

[0046] The polyoxyethylene lauryl amine has a trade designation of NE-1825 and is available from Jiangsu Hai'an Petrochemical Factory;

[0047] The polyoxyethylene lauric acid ester has a trade designation of PEG-400DL and is available from Jiangsu Hai'an Petrochemical Factory;

[0048] The alkylphenol polyoxyethylene polyoxypropylene ether has a trade designation of NPE-108 and is available from Jiangsu Hai'an Petrochemical Factory.

[0049] The preparation method of the oil slurry settling agent of examples 1-4 and comparative examples 1-7 comprises the following steps: mixing the polyether mixture, the solubilizer, the dispersant and the solvent, and stirring uniformly to obtain the oil slurry settling agent.

[0050] Performance test:

[0051] The performance evaluation of the oil slurry settling agent is carried out according to the following steps:

[0052] (1) The oil slurry sample is heated to above the solidification point (about 60°C) in an oven, and is fully shaken, and a certain amount of oil slurry is taken into a flask;

[0053] (2) The oil slurry settling agent is added into the flask, and is placed in a 90°C oil bath, and is mechanically stirred and mixed for 10 minutes;

[0054] (3) The mixed oil slurry is poured into a test tube and is sealed, a thermometer is connected, and is placed in the same constant temperature water bath for natural settling, and the temperature of the oil slurry is controlled to be 85°C-90°C;

[0055] (4) The oil slurry at 20% from the bottom is slowly taken by a pipette after 24h and 48h respectively;

[0056] (5) The taken oil slurry is placed into a crucible with a constant weight, and is placed on an electronic universal furnace, and is ignited by ashless filter paper until no combustible components escape;

[0057] (6) The crucible containing the residue is transferred to a muffle furnace, the temperature of the muffle furnace is controlled to be 750°C-800°C, and is kept constant for 4h;

[0058] (7) After the residue is ashed, the crucible is taken out of the muffle furnace and is placed in the air to cool for 3 minutes, and then is transferred to a desiccator to cool to room temperature, and is weighed by an analytical balance, the data is recorded, and the ash content is calculated.

[0059] Tables 2-4 are the ash removal results of the oil slurry settling agents of examples 1-4 and comparative examples 1-11 on different oil slurry.

[0060] In the following tables 2-4, comparative example 8 is a commercially available oil slurry settling agent with model number JR-SA06; comparative example 9 is a commercially available oil slurry settling agent with model number CK2704A; comparative example 10 is a commercially available oil slurry settling agent with model number CK2704C; and comparative example 11 is a blank control without adding an oil slurry settling agent. The ash content in the Maoming petrochemical oil slurry is 0.488wt% in table 2; the ash content in the Yunnan petrochemical oil slurry is 0.64wt% in table 3; and the ash content in the North China petrochemical oil slurry is 1.18wt% in table 4.

[0061] Table 2 is the ash removal results of the oil slurry settling agents of examples 1-4 and comparative examples 1-11 on the Maoming petrochemical oil slurry (the addition amount is 1000ppm)

[0062]

[0063]

[0064] Table 3 Ash removal results of oil slurry settling agent of examples 1-4 and comparative examples 1-11 on Yunnan petrochemical oil slurry (addition amount 500 ppm)

[0065]

[0066]

[0067]

[0068] Table 4 Ash removal results of oil slurry settling agent of examples 1-4 and comparative examples 1-11 on North China petrochemical oil slurry (addition amount 100 ppm)

[0069]

[0070]

[0071] From the data in Tables 2-4, compared with the three kinds of commercially available oil slurry settling agents of comparative examples 8-10, the oil slurry settling agent of the present application requires a short settling time, has a high settling efficiency, has a high oil slurry ash removal rate in 24 hours, and can reduce the ash content to less than 0.05 wt% in 48 hours. The ash removal rate of the oil slurry settling agent of comparative examples 1-7 is lower than that of the oil slurry settling agent of examples 1-4 of the present application. It can be seen that the oil slurry settling agent provided by the present application has the best effect within the component content range defined in the present application.

[0072] When the oil slurry settling agent of the present application is used, 100 ppm to 1000 ppm of the oil slurry settling agent of the present application is added before the catalytic cracking oil slurry enters the settling tank, mixed uniformly, and settled, and a clarified oil slurry with settled ash can be obtained.

[0073] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and do not limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. An oil slurry settling agent, characterized in that, By mass, it consists of the following raw materials: 25-40 parts of polyether mixture, 10-15 parts of solubilizer, 10-15 parts of dispersant, and 35-50 parts of solvent; The polyether mixture comprises the following components by mass percentage: 25%~35% tallow amine polyoxyethylene ether, 25%~35% polyoxyethylene laurate, and 30%~50% alkylphenol polyoxyethylene polyoxypropylene ether; the dispersant is an oil-soluble phenolic resin with an average molecular weight of 2000~5000.

2. The oil slurry settling agent according to claim 1, characterized in that, The tallow amine polyoxyethylene ether has an HLB value of 2 to 10 and an average molecular weight of 2000 to 8000.

3. The oil slurry settling agent according to claim 1, characterized in that, The polyoxyethylene laurate has an HLB value of 2 to 15 and an average molecular weight of 300 to 1200.

4. The oil slurry settling agent according to claim 1, characterized in that, The alkylphenol polyoxyethylene polyoxypropylene ether has an HLB value of 2 to 15 and an average molecular weight of 1000 to 6000.

5. The oil slurry settling agent according to claim 1, characterized in that, The solubilizer is polypropylene glycol, and the average molecular weight of the polypropylene glycol is 1000~4000.

6. The oil slurry settling agent according to claim 1, characterized in that, The solvent is a high flash point solvent, which is 150# aromatic solvent oil and / or 1800# aromatic solvent oil.

7. The method for preparing the oil slurry settling agent according to any one of claims 1-6, characterized in that, The process includes the following steps: mixing the polyether mixture, solubilizer, dispersant, and solvent, and stirring until homogeneous to obtain the final product.

8. The application of the oil slurry settling agent according to any one of claims 1-6 in the ash settling of oil slurry.

9. The application according to claim 8, characterized in that, Take 100ppm~1000ppm of the oil slurry settling agent and mix it evenly with the oil slurry to obtain the final product.

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