Catalytic cracking multifunctional additive and preparation method thereof

Abstract

The application provides a catalytic cracking multifunctional additive and a preparation method thereof. The catalytic cracking multifunctional additive comprises the following raw materials: 8-30% of a first ligand, 5-30% of a second ligand, 5-25% of a solubilizer, 10-25% of a metal component and 5-30% of water. The preparation method comprises the following steps: adding the first ligand into a solution of a metal component precursor drop by drop, obtaining a first solution after reaction for a period of time; adding the second ligand into the first solution drop by drop, obtaining a second solution after reaction for a period of time; adding the solubilizer into the second solution drop by drop, stirring for a period of time, forming a uniform and stable system, and obtaining the catalytic cracking multifunctional additive. The catalytic cracking multifunctional additive provided by the application can inhibit the pollution of metals such as nickel, vanadium and calcium in the catalytic cracking process, and can also have a synergistic effect with the catalyst, and has a synergistic function.

Description

TECHNICAL FIELD

[0001] The present application relates to a multifunctional catalyst cracking aid and a preparation method thereof, and belongs to the technical field of petroleum and chemical industry. BACKGROUND

[0002] Heavy metals in catalytic cracking raw oil include nickel, vanadium, iron, sodium, calcium, etc., among which the content of nickel and vanadium is the highest and the harm is the most serious. Especially in the case of the increasingly serious trend of poor quality of raw oil, how to solve the pollution of metals in the raw oil to the catalyst is of great significance to the catalytic cracking unit. At the same time, refining enterprises have an urgent need to reduce costs and increase efficiency. Reducing production costs and improving catalyst efficiency has always been one of the key targets of refining enterprises.

[0003] In view of the heavy metal pollution problem in catalytic cracking raw oil, the most widely used method to inhibit heavy metals is to add a metal passivator. The addition amount of the metal passivator can be adjusted in time according to the concentration of nickel, vanadium and other metals in the raw oil, the operation is very flexible, the effect is remarkable, and the investment is small. However, most of the currently marketed metal passivators use toxic antimony and tin as effective components, which poses a safety and environmental risk when used. The waste catalyst produced after using the above metal passivator (containing antimony and tin elements) must be treated as hazardous waste, which increases the difficulty of enterprise management and the cost of hazardous waste treatment. Moreover, such metal passivators are water-soluble and have poor miscibility with catalytic cracking raw oil, and the reaction is not sufficient.

[0004] The most widely used in the market is a single-function antimony-based nickel passivator. As early as the 1970s, Phillips Petroleum Company successfully developed an antimony-based nickel passivator, which was named Phil-Ad-CA, a mineral oil solution of dipropyl dithiophosphoric acid antimony, and was commercialized in 1976 in the FCC unit of Borger. However, this passivator not only has a pungent odor, is difficult to dissolve in general solvents, and will produce a precipitate when exposed to light, which brings great trouble to the filling operation. US4031002A and US4394324A both disclose such a single-function antimony-based nickel passivator. Subsequent researchers have made many improvements to the antimony-based nickel passivator and developed a series of water-soluble antimony-based nickel passivators that are convenient to use and safe to transport. CN1294173A, CN1245198A and CN1176288A all disclose improved antimony-based nickel passivators. Although the addition of antimony-based passivators has a certain limiting effect on nickel-contaminated catalysts, antimony itself is toxic, which seriously affects human health when it is taken out of the device with the product or deposited on the equipment. Moreover, the cost of antimony-based nickel passivators is high, which also limits the large-scale use of antimony-based passivators.

[0005] In addition, the Sb-Sn bifunctional metal passivator for nickel and vanadium pollution is also widely used in the market. The earliest bifunctional metal passivator is the Sb-Sn bifunctional passivator developed by PhiiliPs company. This passivator is a combination of single-function nickel passivator and vanadium passivator. However, when antimony agent and tin agent are used at the same time, not only the toxicity is large, the compounding property is poor, but also the addition amount of CO combustion promoter is increased. Although the subsequent bifunctional metal passivator has been improved, rare earth metals or alkali metals are selected as the vanadium passivator, but the nickel passivation component is still mostly antimony-based passivator, and a separate nickel passivator and vanadium passivator are still mostly selected for compounding, and the preparation method is complicated, and the failure rate is high. CN107159315A selects antimony as the nickel passivator and lanthanum as the vanadium passivator to prepare a bifunctional metal passivator. CN102974400A compounding antimony single agent and cerium single agent obtains a bifunctional metal passivator. CN104841490A uses one or both of antimony trioxide and antimony pentoxide as the nickel passivator, and lanthanum acetate as the vanadium passivator to prepare a bifunctional metal passivator.

[0006] There are also studies on non-antimony, tin system bifunctional metal passivators in the prior art, which basically use non-metallic elements such as boron to replace antimony and tin. The synthesis is complex, and the passivation capacity needs to be improved due to the use of non-metallic elements. CN102974401A selects boron and magnesium as the main effective components to prepare an environmentally friendly multifunctional metal passivator, which is mainly used for inhibiting nickel and vanadium pollution in the catalytic cracking process.

[0007] In addition, the above-mentioned metal passivators can only passivate nickel and vanadium pollution, cannot inhibit calcium pollution, and do not have the synergistic function of the catalytic cracking catalyst.

[0008] Therefore, the existing catalytic cracking passivator has the technical problems of large toxicity, high cost, difficult preparation, poor stability, and single function.

[0009] In summary, in order to replace the traditional catalytic cracking metal passivator, developing a new type of catalytic cracking multifunctional additive has become one of the problems to be solved in the field. SUMMARY

[0010] In order to solve the above technical problems, the purpose of the present application is to provide a catalytic cracking multifunctional additive and a preparation method thereof. The catalytic cracking multifunctional additive provided by the present application can inhibit the pollution of nickel, vanadium, calcium and other metals in the catalytic cracking process, and can also have a synergistic effect with the catalyst, and has a synergistic function.

[0011] To achieve the above object, the present application provides a catalytic cracking multifunctional additive, which comprises the following raw materials in percentage by mass: 8-30% of a first ligand, 5-30% of a second ligand, 5-25% of a solubilizer, 10-25% of a metal component, and 5-30% of water; wherein the first ligand comprises an alcohol compound, the second ligand comprises an ester compound, and the metal component comprises three or more of magnesium, aluminum, cerium, lanthanum, praseodymium, zirconium and yttrium.

[0012] According to the specific embodiment of the present application, preferably, the catalytic cracking multifunctional additive comprises the following raw materials in percentage by mass: 10-25% of the first ligand, 10-25% of the second ligand, 10-20% of the solubilizer, 12-20% of the metal component, and 10-25% of water.

[0013] In the above catalytic cracking multifunctional additive, preferably, the first ligand comprises ethylene glycol and / or glycerol, etc.

[0014] In the above catalytic cracking multifunctional additive, preferably, the second ligand comprises butyl acetate and / or propyl acetate, etc.

[0015] In the above catalytic cracking multifunctional additive, preferably, the solubilizer comprises an amide compound. More preferably, the solubilizer comprises one or a combination of N-methyl formamide, N,N-dimethyl formamide and N,N-dimethyl acetamide, etc.

[0016] In the above catalytic cracking multifunctional additive, preferably, the metal component comprises lanthanum, and two or more of magnesium, aluminum, cerium, praseodymium, zirconium and yttrium.

[0017] In the above catalytic cracking multifunctional additive, preferably, the content of lanthanum in the raw materials of the catalytic cracking multifunctional additive is 2-15% (more preferably 5-10%) by mass percentage, the content of cerium is 0-10% (more preferably 1-5%), the content of aluminum is 0-10% (more preferably 1-5%), the content of magnesium is 0-10% (more preferably 1-5%), the content of praseodymium is 0-10% (more preferably 1-8%), the content of zirconium is 0-10% (more preferably 1-8%), the content of yttrium is 0-10% (more preferably 1-8%), the content of two or more of magnesium, aluminum, cerium, praseodymium, zirconium and yttrium is not 0%, and the total content of the metal component is 10-25% (more preferably 12-20%).

[0018] According to the specific embodiment of the present application, preferably, the catalytic cracking multifunctional additive is prepared by at least the following steps:

[0019] (1) adding the first ligand dropwise to a solution of the metal component precursor while stirring, and allowing the reaction to proceed for a certain period of time to obtain a first solution;

[0020] (2) adding the second ligand dropwise to the first solution while stirring, and allowing the reaction to proceed for a certain period of time to obtain a second solution;

[0021] (3) adding the solubilizing agent dropwise to the second solution while stirring for a certain period of time to form a uniform and stable system, thereby obtaining the catalytic cracking multifunctional aid.

[0022] In the above catalytic cracking multifunctional aid, preferably, in the preparation steps of the catalytic cracking multifunctional aid, the precursor of the metal component in step (1) comprises a soluble salt compound of the metal component, more preferably a nitrate salt.

[0023] In the above catalytic cracking multifunctional aid, preferably, in the preparation steps of the catalytic cracking multifunctional aid, the solution of the precursor of the metal component in step (1) is obtained by mixing the precursor of the metal component with water. More preferably, the mixing temperature is 10°C to 30°C, and further preferably 15°C to 25°C. The mixing step can be carried out under stirring.

[0024] In the above catalytic cracking multifunctional aid, preferably, in the preparation steps of the catalytic cracking multifunctional aid, the dropwise adding speed of the first ligand in step (1) is 1 to 10 drops / 10 s, and more preferably 2 to 8 drops / 10 s.

[0025] In the above catalytic cracking multifunctional aid, preferably, in the preparation steps of the catalytic cracking multifunctional aid, the reaction temperature in step (1) is 40°C to 80°C, and the reaction time is 2 h to 5 h. More preferably, the reaction temperature in step (1) is 45°C to 70°C, and the reaction time is 2 h to 4 h.

[0026] In the above catalytic cracking multifunctional aid, preferably, in the preparation steps of the catalytic cracking multifunctional aid, the dropwise adding speed of the second ligand in step (2) is 1 to 20 drops / 10 s, and more preferably 1 to 10 drops / 10 s.

[0027] In the above catalytic cracking multifunctional aid, preferably, in the preparation steps of the catalytic cracking multifunctional aid, the reaction temperature in step (2) is 80°C to 120°C, and the reaction time is 1 h to 3 h. More preferably, the reaction temperature in step (2) is 90°C to 110°C, and the reaction time is 1 h to 2 h.

[0028] In the catalytic cracking multifunctional additive, preferably, in the preparation step of the catalytic cracking multifunctional additive, the temperature of the stirring in step (3) is 80-120℃, and the time is 0.5-2h. More preferably, the temperature of the stirring in step (3) is 90-110℃, and the time is 0.5-1.5h.

[0029] According to the specific embodiment of the present application, preferably, the density of the catalytic cracking multifunctional additive at 20℃ is 1.00g·cm -3 -2.00g·cm -3 , more preferably 1.15g·cm -3 -1.85g·cm -3 . Wherein, the density of the catalytic cracking multifunctional additive is tested according to GB / 4472-84.

[0030] According to the specific embodiment of the present application, preferably, the kinematic viscosity of the catalytic cracking multifunctional additive at 20℃ is 8.00mm 2 ·s -1 -18.00mm 2 ·s -1 , more preferably 10.00mm 2 ·s -1 -15.00mm 2 ·s -1 . Wherein, the kinematic viscosity of the catalytic cracking multifunctional additive is tested according to GB / T265-88.

[0031] The second aspect of the present application provides a preparation method of the above-mentioned catalytic cracking multifunctional additive, which comprises the following steps:

[0032] (1) adding the first ligand into the solution of the metal component precursor dropwise while stirring, and obtaining a first solution after a period of reaction;

[0033] (2) adding the second ligand into the first solution dropwise while stirring, and obtaining a second solution after a period of reaction;

[0034] (3) adding the solubilizer into the second solution dropwise while stirring for a period of time to form a uniform and stable system, and obtaining the catalytic cracking multifunctional additive.

[0035] In the above preparation method of the present application, first, the first ligand in step (1) is coupled with the precursor of the metal component to obtain a solution containing the complex of the metal component and the first ligand (i.e., the first solution); then, the second ligand in step (2) is further coupled with the complex formed in step (1), and the solubilizing agent in step (3) is used to mainly promote the further coupling of the second ligand with the complex formed in step (1), and also has the effect of strengthening dispersion and solubility, forming the final metal complex, thereby obtaining the catalytic cracking multifunctional additive of the present application.

[0036] In the above preparation method, preferably, the precursor of the metal component in step (1) comprises a soluble salt compound of the metal component, and more preferably, a nitrate salt.

[0037] In the above preparation method, preferably, the solution of the precursor of the metal component in step (1) is obtained by mixing the precursor of the metal component with water. More preferably, the mixing temperature is 10°C to 30°C, and further preferably, 15°C to 25°C. The mixing step can be carried out under stirring.

[0038] In the above preparation method, preferably, the dropping speed of the first ligand in step (1) is 1 to 10 drops per 10 seconds, and more preferably, 2 to 8 drops per 10 seconds.

[0039] In the above preparation method, preferably, the reaction temperature in step (1) is 40°C to 80°C, and the reaction time is 2h to 5h. More preferably, the reaction temperature in step (1) is 45°C to 70°C, and the reaction time is 2h to 4h.

[0040] In the above preparation method, preferably, the dropping speed of the second ligand in step (2) is 1 to 20 drops per 10 seconds, and more preferably, 1 to 10 drops per 10 seconds.

[0041] In the above preparation method, preferably, the reaction temperature in step (2) is 80°C to 120°C, and the reaction time is 1h to 3h. More preferably, the reaction temperature in step (2) is 90°C to 110°C, and the reaction time is 1h to 2h.

[0042] In the above preparation method, preferably, the stirring temperature in step (3) is 80°C to 120°C, and the stirring time is 0.5h to 2h. More preferably, the stirring temperature in step (3) is 90°C to 110°C, and the stirring time is 0.5h to 1.5h.

[0043] The application provides a catalytic cracking multifunctional additive and a preparation method thereof. The catalytic cracking multifunctional additive is prepared through a coordination reaction by using metal components meeting environmental protection requirements as first ligands, using alcohol compounds as second ligands, and using amide compounds as solubilizers. The preparation method of the multifunctional additive avoids the compounding mode of conventional multifunctional metal passivators, has low energy consumption, and is easy to operate. Meanwhile, the catalytic cracking multifunctional additive prepared by the preparation method and the ratio and content of the raw materials has stable performance, can inhibit the pollution of metals such as nickel, vanadium and calcium in the catalytic cracking process, and can have a synergistic effect with the catalyst and has a synergistic effect on the catalyst. The catalytic cracking multifunctional additive is suitable for a catalytic cracking device of oil refining.

[0044] The components of the catalytic cracking multifunctional additive provided by the application are safe and environmentally friendly, and the inhibition mechanism of metal pollution is different from that of traditional antimony and tin-based metal passivators due to the advancement in component selection. The metal components combined with the first ligands and the second ligands make the multifunctional additive of the application have stronger capture ability for Ni and V substances in the raw oil, and the solubility of the multifunctional additive in the raw oil is enhanced, and the reaction performance of the additive is enhanced, so the multifunctional additive of the application has excellent Ni and V pollution inhibition effect, and the effect is better than that of traditional antimony and tin-based metal passivators. In addition, the multifunctional additive of the application can also inhibit Ca pollution. Meanwhile, the multifunctional additive has a synergistic effect with the catalytic cracking catalyst, promotes the activity of the catalyst, improves the product distribution, and improves the total liquid yield. The catalytic cracking multifunctional additive of the application can meet the stable operation and cost reduction and efficiency improvement requirements of the catalytic cracking device of a refining enterprise.

[0045] The technical scheme of the application has at least the following beneficial effects:

[0046] 1. The catalytic cracking multifunctional additive of the application is safe and environmentally friendly. The most widely used antimony and tin-based Ni and V metal passivators on the market are highly toxic, and the use of antimony elements has problems in environmental safety. The catalytic cracking multifunctional additive of the application uses environmentally friendly metal elements as effective components, ensures safe production of enterprises, and solves the problem of subsequent environmental treatment of the catalyst.

[0047] 2. The catalytic cracking multifunctional additive of the application has excellent Ni, V and Ca pollution inhibition performance. The catalytic cracking multifunctional additive has good oil solubility and stronger capture ability for Ni and V in the raw oil due to the use of organic ligands. Compared with not adding the catalytic cracking multifunctional additive, the average decrease of the coke yield is more than 0.7%, and the average decrease of the dry gas yield is more than 0.2% after using the additive, which is better than most antimony and tin-based liquid metal passivators on the market.

[0048] 3、The catalytic cracking multifunctional additive of the present application effectively improves the product distribution of catalytic cracking and increases the total liquid yield. The additive can synergize with the catalyst, promote the activity of the catalyst, improve the product distribution and increase the total liquid yield, which is very important for enterprises to reduce cost and increase efficiency.

[0049] In summary, the catalytic cracking multifunctional additive provided by the present application meets the environmental protection requirements, can inhibit metal pollution and has the functions of increasing efficiency, low cost, simple preparation, stable performance and high efficiency, and can meet the needs of refining enterprises. DETAILED DESCRIPTION

[0050] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail as follows, but cannot be understood as limiting the scope of the present application.

[0051] In the following examples and comparative examples, the performance of the catalytic cracking multifunctional additive is evaluated in the following manner:

[0052] Evaluation device: XTL-5 riser reactor

[0053] The reaction raw material is the raw oil of a 3 million t / a heavy oil catalytic cracking device of Lanzhou Petrochemical Company, and the main properties of the reaction raw material are as follows: relative molecular mass 426 g / mol, density (70℃) 890.6 kg / m 3 , carbon residue mass fraction 3.4%, V content 5.13 μg / g, Fe content 6.83 μg / g, Ca content 4.36 μg / g, Cu content 0.35 μg / g, Ni content 4.35 μg / g, Pb content less than 0.02 μg / g, saturated hydrocarbon mass fraction 58.4%, aromatic hydrocarbon mass fraction 37.2%, and gum mass fraction 4.4%;

[0054] The catalyst used is LDO-75 produced by Lanzhou Petrochemical Company of China Petroleum;

[0055] The specific evaluation conditions are as follows: reaction pressure: atmospheric pressure; reaction temperature: 500℃ (outlet of riser); regeneration temperature: 690℃; oil input: 1.2 kg / h; catalyst / oil ratio: 5-6.5; reaction time: 1.69 s;

[0056] The evaluation experiment uses a one-time injection method, the catalytic cracking multifunctional additive is mixed uniformly with the raw oil, and then continuously sampled and fed into the device; the addition amount of the catalytic cracking multifunctional additive is 150 ppm;

[0057] The gas and liquid compositions of the catalytic cracking products are analyzed by SQ-206 gas chromatography.

[0058] Example 1

[0059] The embodiment provides a catalytic cracking multifunctional additive which is prepared by the following steps:

[0060] (1) 56.5g of aluminum nitrate nonahydrate, 35g of cerium nitrate hexahydrate and 78.5g of lanthanum nitrate hexahydrate are placed in a normal-pressure reaction synthesis device, 50ml of distilled water is slowly added, and the mixture is stirred and uniformly mixed at 10°C to obtain a solution of a metal component precursor;

[0061] (2) 41g of ethylene glycol is slowly added dropwise to the solution of the metal component precursor at a speed of 1 drop / 10s, and the temperature is raised to 40°C while stirring, and the reaction is carried out for 2h to obtain a first solution;

[0062] (3) 46g of butyl acetate is slowly added dropwise to the first solution at a speed of 1 drop / 10s while stirring, the temperature is raised to 80°C, and the reaction is carried out for 1h to obtain a second solution;

[0063] (4) 44ml of N,N-dimethylformamide is added to the second solution, the temperature is kept at 80°C, and the stirring is carried out for 0.5h to form a uniform and stable system, and the catalytic cracking multifunctional additive is obtained.

[0064] The physical and chemical properties of the catalytic cracking multifunctional additive are shown in Table 1.

[0065] After the catalytic cracking multifunctional additive prepared in the embodiment is added into raw oil and runs in a catalytic cracking riser reactor for 18h, the coke yield is reduced by 0.43%, the dry gas yield is reduced by 0.16%, and the total liquid yield is increased by 0.42%, which shows excellent metal contamination inhibition performance and synergistic performance on the catalyst.

[0066] Embodiment 2

[0067] The embodiment provides a catalytic cracking multifunctional additive which is prepared by the following steps:

[0068] (1) 58g of aluminum nitrate nonahydrate, 38g of magnesium nitrate, 86.6g of lanthanum nitrate hexahydrate and 29g of yttrium nitrate are placed in a normal-pressure reaction synthesis device, 50ml of distilled water is slowly added, and the mixture is stirred and uniformly mixed at 25°C to obtain a solution of a metal component precursor;

[0069] (2) A mixture of 45g of ethylene glycol and glycerol (the molar ratio of ethylene glycol to glycerol is 3:2) is slowly added dropwise to the solution of the metal component precursor at a speed of 5 drops / 10s, and the temperature is raised to 50°C while stirring, and the reaction is carried out for 3h to obtain a first solution;

[0070] (3) slowly drop 52 g of a mixture of butyl acetate and propyl acetate (molar ratio of butyl acetate to propyl acetate 1:1) into the first solution at a rate of 10 drops / 10 s while maintaining stirring, and raise the temperature to 110°C for 2 h to obtain a second solution;

[0071] (4) drop 42 ml of N,N-dimethylformamide into the second solution, maintain the temperature at 110°C, and stir for 0.5 h to form a uniform and stable system to obtain the catalytic cracking multifunctional additive.

[0072] The physical and chemical properties of the catalytic cracking multifunctional additive are shown in Table 1.

[0073] After the catalytic cracking multifunctional additive prepared in this example is added into the raw oil and the catalytic cracking riser reactor is operated for 18 h, the coke yield is reduced by 1.06%, the dry gas yield is reduced by 0.41%, and the total liquid yield is increased by 2.05%, showing excellent metal contamination inhibition performance and catalyst synergistic performance.

[0074] Example 3

[0075] This example provides a catalytic cracking multifunctional additive, which is prepared by the following steps:

[0076] (1) Put 44 g of cerium nitrate hexahydrate, 34 g of zirconium nitrate pentahydrate, and 65 g of lanthanum nitrate hexahydrate into a normal pressure reaction synthesis device, slowly add 50 ml of distilled water, stir to mix uniformly at 30°C to obtain a solution of metal component precursors;

[0077] (2) slowly drop 35 g of ethylene glycol into the solution of metal component precursors at a rate of 10 drops / 10 s, and raise the temperature to 50°C while maintaining stirring, and react for 5 h to obtain a first solution;

[0078] (3) slowly drop 38 g of propyl acetate into the first solution at a rate of 20 drops / 10 s while maintaining stirring, and raise the temperature to 90°C for 3 h to obtain a second solution;

[0079] (4) drop 32 ml of N,N-dimethylformamide into the second solution, maintain the temperature at 100°C, and stir for 2 h to form a uniform and stable system to obtain the catalytic cracking multifunctional additive.

[0080] The physical and chemical properties of the catalytic cracking multifunctional additive are shown in Table 1.

[0081] The catalytic cracking multifunctional additive prepared in this example was added into the raw oil, and after running in the catalytic cracking riser reactor for 18 hours, the coke yield was reduced by 0.65%, the dry gas yield was reduced by 0.27%, and the total liquid yield was increased by 1.11%, showing excellent metal contamination inhibition performance and catalyst synergistic performance.

[0082] Example 4

[0083] This example provides a catalytic cracking multifunctional additive, which is prepared by the following steps:

[0084] (1) 30 g of magnesium nitrate, 44 g of praseodymium nitrate hexahydrate, and 53 g of lanthanum nitrate hexahydrate were placed in an atmospheric pressure reaction synthesis device, 35 ml of distilled water was slowly added, and the mixture was stirred uniformly at 20°C to obtain a solution of metal component precursors;

[0085] (2) A mixture of 30 g of ethylene glycol and glycerol (molar ratio of ethylene glycol to glycerol 1:1) was slowly added to the solution of metal component precursors at a rate of 5 drops / 10 s, and the temperature was raised to 60°C while stirring, and the reaction was carried out for 2 h to obtain a first solution;

[0086] (3) A mixture of 36 g of butyl acetate and propyl acetate (molar ratio of butyl acetate to propyl acetate 1:1) was slowly added to the first solution at a rate of 10 drops / 10 s while stirring, and the temperature was raised to 110°C and the reaction was carried out for 2 h to obtain a second solution;

[0087] (4) 30 ml of N,N-dimethylacetamide was added to the second solution, the temperature was maintained at 110°C and stirring was carried out for 0.5 h to form a uniform and stable system, and the catalytic cracking multifunctional additive was obtained.

[0088] The physical and chemical properties of the catalytic cracking multifunctional additive are shown in Table 1.

[0089] The catalytic cracking multifunctional additive prepared in this example was added into the raw oil, and after running in the catalytic cracking riser reactor for 18 hours, the coke yield was reduced by 0.82%, the dry gas yield was reduced by 0.34%, and the total liquid yield was increased by 1.52%, showing excellent metal contamination inhibition performance and catalyst synergistic performance.

[0090] Example 5

[0091] This example provides a catalytic cracking multifunctional additive, which is prepared by the following steps:

[0092] (1) Put 75 g of aluminum nitrate nonahydrate, 43 g of zirconium nitrate pentahydrate and 65 g of lanthanum nitrate hexahydrate into a normal-pressure reaction synthesis device, slowly add 40 ml of distilled water, stir to mix uniformly at 20 °C, and obtain a solution of metal component precursors;

[0093] (2) Slowly drop 30 g of a mixture of ethylene glycol and glycerol (molar ratio of ethylene glycol to glycerol 1:2) into the solution of metal component precursors at a speed of 10 drops / 10 s, and heat to 80 °C while stirring, and react for 2 h to obtain a first solution;

[0094] (3) Slowly drop 48 g of butyl acetate into the first solution at a speed of 15 drops / 10 s while stirring, heat to 120 °C, and react for 1 h to obtain a second solution;

[0095] (4) Drop 37 ml of N-methyl formamide into the second solution, keep the temperature at 120 °C, and stir for 0.5 h to form a uniform and stable system, and obtain the catalytic cracking multifunctional additive.

[0096] The physicochemical properties of the catalytic cracking multifunctional additive are shown in Table 1.

[0097] After the catalytic cracking multifunctional additive prepared in this example is added into raw oil and runs in a catalytic cracking riser reactor for 18 h, the coke yield is reduced by 0.57%, the dry gas yield is reduced by 0.26%, and the total liquid yield is increased by 1.25%, showing excellent metal contamination inhibition performance and synergistic performance for catalysts.

[0098] Table 1 Physicochemical properties of catalytic cracking multifunctional additives prepared in Examples 1-5

[0099]

[0100] Comparative Example 1

[0101] This comparative example provides a catalytic cracking multifunctional additive, which is prepared by the following steps:

[0102] (1) Put 30 g of magnesium nitrate, 44 g of praseodymium nitrate hexahydrate and 53 g of lanthanum nitrate hexahydrate into a normal-pressure reaction synthesis device, slowly add 35 ml of distilled water, stir to mix uniformly at 20 °C, and obtain a solution of metal component precursors;

[0103] (2) Slowly drop 58 g of a mixture of butyl acetate and propyl acetate (molar ratio of butyl acetate to propyl acetate 1:1) into the solution of metal component precursors at a speed of 10 drops / 10 s while stirring, heat to 110 °C, and react for 2 h to obtain a mixed solution;

[0104] (3) 30 ml of N,N-dimethylacetamide was added dropwise into the mixed solution, the temperature was kept at 110°C and stirred for 0.5 h to form a uniform and stable system, and the catalytic cracking multifunctional additive was obtained.

[0105] The physical and chemical properties of the catalytic cracking multifunctional additive are shown in Table 2.

[0106] The catalytic cracking multifunctional additive prepared in the present example was added into the raw oil, and after running in the catalytic cracking riser reactor for 18 h, the coke yield increased by 0.16%, the dry gas yield increased by 0.21%, and the total liquid yield decreased by 0.34%. The reason for the poor performance of the additive in the present example is speculated to be that the metal component cannot form a complex well although the amount of the second ligand is increased, and the uncomplexed metal ions agglomerate on the surface of the catalyst, which affects the performance of the catalyst.

[0107] Comparative Example 2

[0108] The present example provides a catalytic cracking multifunctional additive, which is prepared by the following steps:

[0109] (1) 30 g of magnesium nitrate, 44 g of praseodymium nitrate hexahydrate and 53 g of lanthanum nitrate hexahydrate were placed in an atmospheric pressure reaction synthesis device, 35 ml of distilled water was slowly added, and the mixture was stirred uniformly at 20°C to obtain a solution of metal component precursors;

[0110] (2) 30 g of a mixture of ethylene glycol and glycerol (molar ratio of ethylene glycol to glycerol 1:1) was slowly added dropwise to the solution of metal component precursors at a rate of 5 drops / 10 s, and the temperature was raised to 60°C while stirring, and the reaction was carried out for 2 h to obtain a first solution;

[0111] (3) 30 ml of N,N-dimethylacetamide was added dropwise into the first solution, the temperature was raised to 110°C and stirred for 0.5 h to form a uniform and stable system, and the catalytic cracking multifunctional additive was obtained.

[0112] The physical and chemical properties of the catalytic cracking multifunctional additive are shown in Table 2.

[0113] The catalytic cracking multifunctional additive prepared in the present example was added into the raw oil, and after running in the catalytic cracking riser reactor for 18 h, the coke yield increased by 0.16%, the dry gas yield increased by 0.21%, and the total liquid yield decreased by 0.34%. The reason for the poor performance of the additive in the present example is speculated to be that the metal component cannot form a complex well although the amount of the second ligand is increased, and the uncomplexed metal ions agglomerate on the surface of the catalyst, which affects the performance of the catalyst.

[0114] Table 2 physical and chemical properties of the catalytic cracking multifunctional additives prepared in Comparative Examples 1-2

[0115]

[0116] In conclusion, the catalytic cracking multifunctional additive provided by the present application meets the environmental protection requirements, can inhibit metal contamination, has a synergistic effect on catalysts, has the advantages of low cost, simple preparation, stable performance, high efficiency, and the like, and can meet the needs of refining enterprises.

Claims

1. A multifunctional catalytic cracking additive, comprising, by weight percentage: 8%–30% of a first ligand, 5%–30% of a second ligand, 5%–25% of a solubilizer, 10%–25% of a metal component, and 5%–30% of water; wherein, The first ligand comprises an alcohol compound, the second ligand comprises an ester compound, the solubilizer comprises an amide compound, and the metal component comprises three or more of magnesium, aluminum, cerium, lanthanum, praseodymium, zirconium, and yttrium.

2. The multifunctional catalytic cracking additive according to claim 1, wherein, The catalytic cracking multifunctional additive comprises the following raw materials by weight percentage: The first ligand is 10%–25%, the second ligand is 10%–25%, the solubilizer is 10%–20%, the metal component is 12%–20%, and the water is 10%–25%.

3. The multifunctional catalytic cracking additive according to claim 1 or 2, wherein, The first ligand includes ethylene glycol and / or glycerol.

4. The multifunctional catalytic cracking additive according to claim 1 or 2, wherein, The second ligand includes butyl acetate and / or propyl acetate.

5. The catalytic cracking multifunctional additive according to claim 1 or 2, wherein, The solubilizer includes one or a combination of N-methylformamide, N,N-dimethylformamide and N,N-dimethylacetamide.

6. The multifunctional catalytic cracking additive according to claim 1 or 2, wherein, The metallic component includes lanthanum, and two or more of magnesium, aluminum, cerium, praseodymium, zirconium, and yttrium.

7. The multifunctional catalytic cracking additive according to claim 6, wherein, By mass percentage, the raw material of the catalytic cracking multifunctional additive contains 2%–15% lanthanum, 0%–10% cerium, 0%–10% aluminum, 0%–10% magnesium, 0%–10% praseodymium, 0%–10% zirconium, and 0%–10% yttrium, and the content of two or more of magnesium, aluminum, cerium, praseodymium, zirconium, and yttrium is not 0%, and the total content of the metal components is 10%–25%.

8. The multifunctional catalytic cracking additive according to claim 1, wherein, The density of the catalytic cracking multifunctional additive at 20°C is 1.00 g·cm³. -3 ~2.00g·cm -3 .

9. The multifunctional catalytic cracking additive according to claim 8, wherein, The density of the catalytic cracking multifunctional additive at 20°C is 1.15 g·cm³. -3 ~1.85g·cm -3 .

10. The multifunctional catalytic cracking additive according to claim 1, wherein, The kinematic viscosity of the catalytic cracking multifunctional additive at 20°C is 8.00 mm. 2 ·s -1 ~18.00mm 2 ·s -1 .

11. The multifunctional catalytic cracking additive according to claim 10, wherein, The kinematic viscosity of the catalytic cracking multifunctional additive at 20°C is 10.00 mm. 2 ·s -1 ~15.00mm 2 ·s -1 .

12. A method for preparing the catalytic cracking multifunctional additive according to any one of claims 1-11, comprising the following steps: (1) The first ligand is added dropwise to the solution of the metal component precursor while stirring. After reacting for a period of time, a first solution is obtained. (2) The second ligand is added dropwise to the first solution while stirring. After reacting for a period of time, a second solution is obtained. (3) Add the solubilizer dropwise to the second solution and stir for a period of time to form a homogeneous and stable system, thereby obtaining the multifunctional catalytic cracking additive.

13. The preparation method according to claim 12, wherein, The precursor of the metal component in step (1) includes soluble salt compounds of the metal component.

14. The preparation method according to claim 13, wherein, In step (1), the precursor of the metal component includes the nitrate of the metal component.

15. The preparation method according to claim 12, wherein, In step (1), the dropping rate of the first ligand is 1 to 10 drops / 10 s.

16. The preparation method according to claim 12, wherein, The reaction temperature in step (1) is 40℃~80℃ and the time is 2h~5h.

17. The preparation method according to claim 12, wherein, In step (2), the dropping rate of the second ligand is 1 to 20 drops / 10s.

18. The preparation method according to claim 12, wherein, The reaction temperature in step (2) is 80℃~120℃ and the time is 1h~3h.

19. The preparation method according to claim 12, wherein, The stirring temperature in step (3) is 80℃~120℃, and the stirring time is 0.5h~2h.

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