A flexible environment-friendly filter material for separating catalytic cracking slurry concentrate and a preparation method thereof

Abstract

The application discloses a preparation method of a flexible environment-friendly filter material for separating a catalytic cracking slurry concentrate, and belongs to the technical field of petroleum chemical industry, and comprises the following steps: S1, modifying a hard biomass material after being crushed in an acid solution to obtain an activated modified product; and S2, co-grinding the activated modified product with a particle capturing agent and then drying to obtain the filter material; the natural biomass is used as a raw material, surface modification and compounding are carried out, the solid content of the catalytic cracking slurry concentrate can be effectively reduced, and the oil-soluble salt in the catalytic cracking slurry concentrate can be removed, so that the catalytic cracking slurry concentrate which can only be treated as hazardous waste at present is converted into a marine fuel blending component; and the technology has the advantages of low manufacturing cost, strong raw material adaptability, high oil product yield of the recovered concentrate, and high solid removal rate.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of petroleum chemical industry, and particularly relates to a flexible environment-friendly filter material for separating catalytic cracking slurry concentrate and a preparation method thereof. BACKGROUND

[0002] Catalytic cracking is the most commonly used technology in the petroleum secondary processing industry. There are more than 180 catalytic cracking devices of different types in China, with a processing capacity of 216 million tons. Catalytic slurry accounts for about 5-10% of the catalytic cracking processing capacity. As a byproduct of catalytic cracking, catalytic slurry is rich in aromatic hydrocarbons (three, four rings and short side chain aromatic hydrocarbons), has low gum and asphaltene content, has high economic utilization value and good market prospects, and can produce high value-added products such as needle coke, high-end carbon materials, lithium ion negative electrode materials, marine fuel oil and rubber filling oil. Due to the presence of a large amount of catalyst solid particles, the separation difficulty limits its application range.

[0003] At present, the oil slurry purification separation methods include electrostatic separation method, chemical sedimentation method, high-temperature centrifugal separation method, metal filter core filtration method and inorganic membrane filtration method. Patent CN112480959B discloses a method for removing solid impurities from catalytic slurry at low temperature. The method comprises the following steps: heating, dehydration, adding liquid additive mixture, heating solid additive mixture, and solid-liquid separation, thereby obtaining purified catalytic slurry with low ash content after removing solid impurities. Through the combined action of liquid additives and solid additives, small catalyst solid particles are coalesced into large particles, thereby removing impurities; the liquid additive is a liquid mixture comprising a dispersing agent, an oil repellent and a diluent. The weight proportions of the dispersing agent, the oil repellent and the diluent are 10-20%, 20-40% and 40-60%, respectively; the solid additive is a solid mixture comprising a nucleating agent, a fine particle trapping agent and a filter aid, and the weight proportions of the nucleating agent, the fine particle trapping agent and the filter aid are 20-30%, 30-50% and 30-50%, respectively; the solid impurities in the catalytic slurry are separated in solid form, the process technology is novel and easy to operate, and continuous separation can be realized; patent CN114540073A discloses a method for removing catalyst particles from catalytic cracking slurry. The treatment method comprises the following steps: preheating the catalytic cracking slurry; adding a flocculating agent and a weighting agent to solvent water to prepare a sedimentation aid, and adding the preheated catalytic cracking slurry to the mixture, emulsifying the mixture by shearing to obtain emulsified slurry; the emulsified slurry is continuously subjected to static sedimentation separation under the conditions of 110-200℃ and a pressure of 0.2-1.3MPa, and the mixture of separated catalyst particles and water is discharged; the method is suitable for various oil slurry with different properties, has small investment, low operation cost and high removal rate, and can reduce the ash content in the catalytic slurry to below 0.005wt%.

[0004] In industrial production, filtration method and electrostatic separation method are commonly used, but these two methods will produce a certain amount of high-concentration catalyst fine powder oil slurry concentrate, usually the yield of oil slurry concentrate accounts for 5%-10% of the oil slurry treatment amount, because of high asphaltene content, high viscosity and high catalyst fine powder content (2-10%), separation is extremely difficult; in addition, oil slurry concentrate itself is a hazardous waste product, the treatment cost is high, which affects the economic benefit and safety production of the device. Therefore, removing the solid particles in the catalytic cracking oil slurry concentrate and realizing the resource utilization of waste are crucial for the development of oil slurry industry chain of oil refining enterprises.

[0005] At present, there are few methods for treating oil slurry concentrate, and there is no mature treatment process, which affects the resource utilization and high-value utilization of catalytic cracking oil slurry in oil refineries. In the prior art, when separating the catalyst in the catalytic cracking oil slurry, a large number of chemical additives are used, which are all compositions, increasing the cost and complexity of the additives, and there are problems of high production cost, large energy consumption in the separation process and low separation efficiency. SUMMARY

[0006] In view of at least one of the above problems, the present application provides a flexible and environmentally friendly filter material for separating catalytic cracking oil slurry concentrate and a preparation method thereof.

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

[0008] A preparation method of a flexible and environmentally friendly filter material for separating catalytic cracking oil slurry concentrate, comprising the following steps:

[0009] S1, after the hard biomass material is crushed, it is modified in an acid solution, the acid modification treatment can activate the oxygen-containing groups on the surface of the biomass material, and an activated modified product is obtained;

[0010] S2, after the activated modified product is co-ground with a particle capturing agent, it is dried to obtain.

[0011] Preferably, the hard biomass material is hard plant stem and / or plant fruit shell.

[0012] The plant stem includes pine, oak and the like, and the plant fruit shell includes oil tea fruit shell, coconut shell, walnut shell and the like.

[0013] Preferably, the particle capturing agent is one or more of marble, limestone, diatomite and kaolin.

[0014] Preferably, in the environmentally friendly filter material, the proportion of the particle capturing agent is 5-10%, and the proportion of the natural biomass material is 90-95%.

[0015] Preferably, the particle size of the environmentally friendly filter material is 5-500 pm.

[0016] Preferably, the acid solution is an organic acid and / or an inorganic acid, the temperature of the modification treatment is 30-50 DEG C, and the time of the modification treatment is 20-30 min.

[0017] Preferably, the organic acid is acetic acid, and the inorganic acid is phosphoric acid; more preferably, the acid is a mixed acid of dilute phosphoric acid and acetic acid, the concentration of the dilute phosphoric acid is 0.01-0.1 mol / L, and the weight proportion of acetic acid in the mixed acid is 5-40%.

[0018] Preferably, the drying temperature is 100-120 DEG C, and the drying time is 30-60 min.

[0019] Another aspect of the present application provides a flexible and environmentally friendly filter material for separating a catalytic cracking slurry concentrate, wherein the filter material is prepared by the above method.

[0020] The flexible filter material has the following advantages: the size of catalyst fine powder in the slurry is 10 nm-10 μm, the main components are SiO2 and Al2O3, and the filter material can easily block the filter channel, the filter material is based on a crushed body of wood or similar hard plants, and the filter material can be added into the slurry to interact with the catalyst fine powder and support the framework, and the filter material has a similar "breathing effect", can improve the filter flow and reduce the pressure drop.

[0021] The present application also provides a method for using the flexible and environmentally friendly filter material, which comprises the following steps: mixing the filter material with a catalytic cracking slurry concentrate, and then performing pressure filtration separation, such as plate and frame pressure filtration, to discharge blocky filter residue through air back flushing and machine cleaning, and to obtain a catalytic cracking slurry with low ash content; or the filter material can be used for suction filtration separation; meanwhile, the blocky filter residue can be used as a resource, specifically, the blocky filter residue is crushed together with coal and sent to a CFB boiler for combustion treatment, and no oily solid waste is generated in the separation process.

[0022] The action mechanism of the flexible and environmentally friendly filter material includes: resistance interception, when the catalytic cracking slurry concentrate containing catalyst particles is in contact with the filter material, catalyst fine powder with a large particle size is first intercepted on the surface of the filter cloth to form a filter cake and play an important filtering role; and adhesion mechanism, the filter material is obtained by embedding a particle capturing agent on the surface of a biomass crushed body through mechanical grinding, when small particles are in contact with the particle capturing agent on the filter material, they are adhered to the surface of the filter material by the action of one or more of van der Waals force, surface tension and Coulomb force, thereby adsorbing and agglomerating the fine catalyst, and the agglomerated catalyst has strong adsorption performance.

[0023] Preferably, the mixing temperature of the flexible and environmentally friendly filter material and the catalytic cracking slurry concentrate is 80-90 DEG C.

[0024] Preferably, the filter cloth used in the filter pressing is made of a mixture of polypropylene and polyester, and has a double-layer structure. The porosity of the filter cloth is matched with the size of the filter material.

[0025] Preferably, the operation temperature of the filter pressing is 110-145 DEG C, the operation pressure is 0.1-0.5 MPa, and the filter pressing time is 2-10 h.

[0026] Preferably, the mixing ratio of the block-shaped filter residue in the coal is 1-5%.

[0027] The present application has the following advantages:

[0028] In view of the defects of the existing concentrated liquid oil slurry treatment method, the present application provides a flexible and environmentally-friendly filter material for separating the concentrated liquid of catalytic cracking oil slurry. The filter material is made of natural biomass, and can effectively reduce the solid content of the concentrated liquid of catalytic cracking oil slurry through surface modification and compounding, and can remove the oil-soluble salt in the concentrated liquid of catalytic cracking oil slurry. The technology has the advantages of low manufacturing cost, strong raw material adaptability, high oil product yield of the concentrated liquid, and high solid removal rate. The yield of the purified concentrated liquid after separation is more than 90%, the yield of the purified catalytic cracking oil slurry after purification is more than 98% when applied to the FCC oil slurry system, the operation pressure of the filter press is reduced, the operation time is prolonged, the block-shaped filter cake can be mixed with coal and sent to a CFB boiler for combustion treatment, no flushing liquid and solid waste are generated during the production process, no additional treatment facilities for waste oil and solid waste are needed, and the technology can create considerable economic and social benefits for enterprises, and has important significance for industrial production and application. BRIEF DESCRIPTION OF DRAWINGS

[0029] The present application is further described by using the drawings, but the embodiments in the drawings do not constitute any limitation on the present application. Other drawings can be obtained by those skilled in the art without creative labor on the basis of the following drawings.

[0030] Figure 1 is a whole picture of the filter material described in embodiment 1 of the present application;

[0031] Figure 2 is a picture showing the agglomeration of catalyst fine powder particles around the filter material in the formation of filter cake during the filtration of the filter material described in embodiment 1 of the present application;

[0032] Figure 3 is a polarizing microscope picture of the oil slurry concentrated liquid before filtration in the embodiment;

[0033] Figure 4 is a polarizing microscope picture of the oil slurry concentrated liquid after filtration in the embodiment;

[0034] Figure 5 is an appearance picture of the filter cake after suction filtration in embodiment 2;

[0035] Figure 6 Figure is the appearance picture (left) and surface SEM picture (right) of the filter cake after Example 3 filtration (pressure filtration), which shows the catalyst fine powder adsorbed on the surface of the filter material;

[0036] Figure 7 Figure is the ash content determination results of the concentrated liquid before and after Example 3 filtration. DETAILED DESCRIPTION

[0037] The application will be further described in combination with the following examples.

[0038] Example 1

[0039] This example relates to a flexible and environmentally friendly filter material for separating catalytic cracking slurry oil concentrate, and the preparation method thereof comprises the following steps:

[0040] S1, mix the dry stem, branch log of pine / oak and oil tea fruit shell according to the ratio (fruit shell accounts for 20%), crush, screen and select the crushed product of 5-500 μm, add to the mixed solution of dilute phosphoric acid (0.02M) and acetic acid (acetic acid content 20%) for acid modification treatment, the treatment temperature is 40℃, the treatment time is 30 min, and the activated modified product is obtained;

[0041] S2, mix the activated modified product with inorganic minerals (diatomite / kaolin) in a ball mill, the addition amount of the inorganic minerals is 5% (m / m) of the crushed product, and dry at 100-120℃ for 60 min to obtain.

[0042] The corresponding relationship between the addition amount of the flexible and environmentally friendly filter material in the certain slurry concentrate and the filtration time is shown in Table 1.

[0043] Table 1 shows the corresponding relationship between the flexible and environmentally friendly filter material and the filtration time.

[0044]

[0045]

[0046] Example 2

[0047] This example uses the catalytic slurry concentrate of a certain petrochemical enterprise, and the specific properties are shown in Table 2.

[0048] Table 2 shows the basic properties of the catalytic cracking slurry concentrate of a certain petrochemical enterprise.

[0049] Item Data Test method Density (20°C), g / cm 3 ]] 1.047 GB / T 1884 Kinematic viscosity (50°C), mm 2 / s]]> 94.2 GB / T 11137 Flash point (closed cup), °C 154 GB / T 261 Ash, % (m / m) 2.35 GB / T 508 Metal elements Al, % (m / m) 0.421 Energy dispersive X-ray fluorescence Si, % (m / m) 0.343 Energy dispersive X-ray fluorescence K, mg / Kg 95 Energy dispersive X-ray fluorescence Cu, mg / Kg 58 Energy dispersive X-ray fluorescence Fe, mg / Kg 40 Energy dispersive X-ray fluorescence Co, mg / Kg 27 Energy dispersive X-ray fluorescence Ca, mg / Kg 23 Energy dispersive X-ray fluorescence Mn, mg / Kg 21 Energy dispersive X-ray fluorescence

[0050] In 200 g of the catalytic cracking concentrate, 1% of the flexible environmental filter material described in Example 1 was added, mixed at 90°C for 20 min, heated to 135°C, and added to a vacuum Buchner funnel filtration device. After filtration for 10 min, oil slurry and filter cake were obtained, respectively, and the filter cake was analyzed as shown in Table 2. Figure 5

[0051] The yield of the filtered oil slurry was 93.4%, the ash content of the filtered oil slurry was 0.0075% (m / m), the Al content in the filtered oil slurry was 15 mg / kg, the Si content was 13 mg / kg, the K content was 14 mg / kg, the Cu content was 7 mg / kg, the Fe content was 10 mg / kg, the Co content was 3 mg / kg, the Mn content was 4 mg / kg, and the Zn content was 3 mg / kg.

[0052] Example 3

[0053] In this example, a catalytic oil slurry concentrate with very high solid content from a petrochemical enterprise was used, and the specific properties are shown in Table 3.

[0054] Table 3 Basic properties of the catalytic cracking oil slurry concentrate II from a petrochemical enterprise

[0055] Item Data Test method Density (20°C), g / cm 3 ]] 1.1265 GB / T 1884 Kinematic viscosity (50°C), mm 2 / s]]> 59.5 GB / T 11137 Flash point (closed cup), °C 165 GB / T 261 Ash, % (m / m) 8.99％ GB / T 508 Metal elements Al, % (m / m) 1.588 Energy dispersive X-ray fluorescence Si, % (m / m) 1.394 Energy dispersive X-ray fluorescence

[0056] In 200 g of the catalytic cracking concentrate, 1% of the flexible environmental filter material was added, mixed at 90°C for 20 min, heated to 130°C, and added to a vacuum Buchner funnel filtration device. After filtration for 10 min, the filter cake and the filter material surface adsorbed catalyst fines after filtration were analyzed as shown in Table 4. Figure 6 Figure 7

[0057] The yield of the filtered oil slurry was 84.2%, the ash content of the filtered oil slurry was 0.0089% (m / m), the deashing rate was 99.9%, and the Al+Si content was less than 30 ppm.

[0058] Comparative Example

[0059] In 200 g of the catalytic cracking concentrate, 1% of the filter material with different particle capture agent contents or only the particle capture agent was added, (the activated modified product, the particle capture agent were the same as in Example 1), mixed at 90°C for 20 min, heated to 130°C, and added to a vacuum Buchner funnel filtration device. After filtration for 10 min, the ash content of the concentrate before and after filtration was measured as shown in Table 4.

[0060] Table 4 Comparison of filtration performance of biomass filter material and particle capture agent

[0061] Oil slurry / g Filter material addition amount / g Particulate trap agent / g Ash / % 200 0 0.1 0.4225 200 2 0 0.0281 200 2 0.02 0.0145 200 2 0.06 0.0089 200 2 0.08 0.0072

[0062] ​​​It should be pointed out finally that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to 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 equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A method for preparing a flexible and environmentally friendly filter material for separating catalytic cracking oil slurry concentrate, characterized in that, Includes the following steps: S1. Hard biomass materials are crushed and then modified in an acid solution to obtain activated modified products; S2. The activated modified product is prepared by co-grinding and drying the particulate capture agent. The hard biomass material is hard plant stem and / or plant husk; The particulate capture agent is one of marble, limestone, diatomaceous earth, kaolin, or a combination thereof; In the environmentally friendly filter material, the proportion of the particulate trap is 5-10%, and the proportion of the biomass material is 90-95%. The particle size of the environmentally friendly filter material is 5-500μm; The acid solution is an organic acid and / or an inorganic acid, the temperature of the modification treatment is 30-50℃, and the time of the modification treatment is 20-30 minutes.

2. The method for preparing a flexible environmentally friendly filter material for separating catalytic cracking slurry concentrate according to claim 1, characterized in that, The organic acid is acetic acid, and the inorganic acid is phosphoric acid.

3. The method for preparing a flexible environmentally friendly filter material for separating catalytic cracking slurry concentrate according to claim 1, characterized in that, The drying temperature is 100-120℃, and the drying time is 30-60 minutes.

4. Flexible environmentally friendly filter material prepared by the preparation method according to any one of claims 1-3.

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