Fuel oil stabilizers for high viscosity residue blending, their preparation and use

Abstract

The application discloses a fuel oil stabilizer for high-viscosity residual oil blending. The fuel oil stabilizer comprises, in percentage by weight, 1-15% of a fatty amine, 0.1-1.5% of a mono-polyisobutene bis-succinimide, 0.1-2% of a non-ionic surfactant alkylphenol polyoxyethylene-polyoxypropylene alcohol ether, 1-30% of alkyl imidazole ionic liquid and / or quaternary ammonium salt ionic liquid, 10-30% of polyvinyl pyrrolidone, 10-20% of an antifoaming agent, and the rest of hydrogenated white oil. The stabilizer has good compatibility, dispersibility, aging resistance and thermal stability for high-viscosity residual oil blending fuel oil.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fuel oil blending, and particularly relates to a fuel oil stabilizer for high-viscosity residual oil blending, preparation and application thereof. BACKGROUND

[0002] In China, traditional fuel oil production is mostly based on straight-run and vacuum distillation residual oil as base raw materials, which are blended with heavy distillates on the production line. In recent years, in order to reduce the blending cost, oil slurry and shale oil are used as base raw materials, which are blended with residual oil and asphalt. Such raw materials contain high-molecular-weight condensed aromatic asphaltene with heteroatoms, which can precipitate and deposit during oil transportation, storage and use, resulting in adverse consequences.

[0003] Patent CN201911247079.7 discloses a liquid hydrocarbon marine fuel oil, which contains a marine distillate fuel or a heavy fuel oil or a blend thereof, and contains an additive combination, the additive combination contains: (A) a polyalkenyl-substituted carboxylic acid or anhydride, and (B) a metal hydrocarbyl-substituted hydroxybenzoate and / or sulfonate detergent, wherein the mass ratio of (A) to (B) is in the range of 20:1 to 1:20.

[0004] Patent CN202011570945.9 discloses a marine fuel oil stability aid and a preparation method thereof. The fuel oil stability aid is a modified alkyl phenol polyether amide structure, and the preparation method comprises the following steps: first, alkyl phenol polyoxyethylene ether with m epoxy groups is alkalinized at 45-50 DEG C under stirring for 2 hours, then acetone is added, and under uniform stirring, SN2 nucleophilic substitution reaction is carried out for 4-5 hours by adding chloroacetic acid, after the reaction is completed, the acetone is removed, and a light yellow viscous alkyl phenol polyoxyethylene ether carboxylate is obtained, and the alkyl phenol polyoxyethylene ether carboxylic acid is separated by acid washing; then the alkyl phenol polyoxyethylene ether carboxylic acid and diethylene triamine are heated and blended in a molar ratio of 1:1.0-1:1.2, further esterification reaction is carried out with toluene as a water-carrying agent and p-toluene sulfonic acid as a catalyst, and the alkyl phenol polyether amide is obtained by heating and stirring at 130-145 DEG C for 3-4 hours.

[0005] In order to improve the long-time stability of high-viscosity residual oil during blending, a fuel oil stabilizer for high-viscosity residual oil blending needs to be developed. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application aims to provide a fuel oil stabilizer for high-viscosity residual oil blending and a preparation method thereof. The stabilizer has the characteristics of emulsification, solubilization and anti-coking, and has the effects of improving the thermal storage stability of thick oil, improving the compatibility with other components, and improving the stability of blended fuel oil.

[0007] According to a first aspect of the present application, the present application provides a fuel oil stabilizer for high-viscosity residual oil blending.

[0008] A fuel oil stabilizer for high-viscosity residual oil blending, comprising, in percentage by weight: 1-15% of fatty amine, 0.1-1.5% of mono-polyisobutene bis-succinimide, 0.1-2% of alkyl phenol polyoxyethylene-polyoxypropylene alcohol ether, 1-30% of alkyl imidazole ionic liquid and / or quaternary ammonium salt ionic liquid, 10-30% of polyvinyl pyrrolidone, 10-20% of defoaming agent, and the rest being hydrogenated white oil.

[0009] In the present application, the fatty amine is a primary amine, preferably ethylenediamine, propylenediamine, butylenediamine or hexylenediamine.

[0010] In the present application, the polyisobutene bis-succinimide is mono-polyisobutene bis-succinimide.

[0011] In the present application, the alkyl phenol in the alkyl phenol polyoxyethylene-polyoxypropylene alcohol ether is an alkyl with a carbon number of 8-18. In the block copolymer molecule, the addition number ratio of polyoxyethylene and polyoxypropylene is 50:50-95:5, and the polymerization degree n of polyoxyethylene group (-(CH2CH2O) n ) is 10-90.

[0012] In the present application, the anion of the alkyl imidazole ionic liquid and / or quaternary ammonium salt ionic liquid can be halide ion, tetrafluoroborate ion, sulfate ion or hexafluoroborate ion.

[0013] In the present application, the hydrogenated white oil is an industrial-grade white oil with a grade of 5#, 7#, 10#, 15#, 22#, 32#, 46#, 68#, and one or more of them can be used.

[0014] The principle of the blended fuel oil stabilizer of the present application is: in view of the problems of high viscosity residue oil, such as high viscosity, high content of asphaltene and resin, and deposition and stratification when blended with light oil components, a composite stabilizer is designed by using emulsification, dispersion measures and the principle of multiple additive compounding. The fatty amine has a certain emulsification effect on the asphaltene in the high viscosity residue oil, can improve the pH value of the composite stabilizer, and can improve the overall compounding effect. The mono-polyisobutene bis-succinimide plays the role of dispersant and solubilizer in the high viscosity residue oil system, can effectively prevent coking of the oil during heating, and reduce the generation of sediment. The non-ionic surfactant alkylphenol polyoxyethylene polyoxypropylene alcohol ether has the effect of emulsifying and reducing the viscosity of the high viscosity residue oil, is conducive to the mixing of the high viscosity residue oil with other oil products, and has a synergistic effect with the fatty amine, and can effectively improve the emulsification degree of the thick oil. The hydrogenated white oil as a solvent oil has the characteristics of small viscosity, low pour point, especially high flash point (closed), stable properties, and high temperature resistance, and is an excellent solvent for the stabilizer. The ionic liquid is used as a solvent with synergistic effect, which can increase the mixing compatibility of various reagents in the mixing process by using its strong polarity, and can provide better dispersity by using the steric hindrance of the ionic group.

[0015] According to a second aspect of the present application, the present application further provides a preparation method of the above-mentioned fuel oil stabilizer.

[0016] Specifically, the preparation method of the above-mentioned fuel oil stabilizer comprises the following contents:

[0017] (1) The ionic liquid is heated to a temperature T1, and then polyvinylpyrrolidone and a defoaming agent are added and stirred uniformly to obtain a solution A;

[0018] (2) The fatty primary amine is dissolved in the solution A at the temperature T1, and is stirred uniformly to obtain a solution B;

[0019] (3) The hydrogenated white oil is heated to a temperature T2 and continuously stirred, the mono-polyisobutene bis-succinimide is first added, the alkylphenol polyoxyethylene polyoxypropylene alcohol ether is added after uniform mixing, and the mixture is stirred uniformly at the temperature T2 to obtain a mixed solution C;

[0020] (4) The solution B and the solution C are mixed at a temperature T3, and are stirred for 1.5-3 hours;

[0021] (5) After the stirring is completed, the solution is filtered to obtain the fuel oil stabilizer.

[0022] Further, T1 is 60-100℃; T2 is 40-60℃; and T3 is 25-40℃.

[0023] According to a third aspect of the present application, the present application further provides an application method of the above-mentioned fuel oil stabilizer.

[0024] The application method specifically comprises the following steps:

[0025] (a) heating the high-viscosity residual oil to t1, after the high-viscosity residual oil has good fluidity, adding a stabilizer, stirring uniformly to obtain component oil M;

[0026] (b) reducing the temperature of the component oil M to t2, adding a part of light component oil under stirring, continuously stirring for 30-90 min to obtain component oil N which is fully emulsified and reduced in viscosity;

[0027] (c) fully mixing the remaining part of the light component oil in the component oil N at temperature t3, stirring for more than 30 min to obtain a blended fuel oil product.

[0028] Further, the temperature t1 is in the range of 80-180 DEG C, the temperature t2 is in the range of 50-80 DEG C, and the temperature t3 is in the range of room temperature-50 DEG C.

[0029] Further, the high-viscosity residual oil has a kinematic viscosity of not less than 8000 mm 2 / s at 50 DEG C, a density of not more than 0.98 g / cm 3 at 20 DEG C, and a sulfur content of not more than 0.5 wt%.

[0030] Further, the light component oil can be selected from one or more of catalytic diesel oil, coal diesel, shale oil, hydrorefined wax oil, rubber cracking oil, and mixed oil of C9 and C10. The light component oil has a kinematic viscosity of 1.0-40 mm 2 / s at 50 DEG C, a density of 0.9570-0.9810 g / cm 3 at 20 DEG C, and a moisture content of not more than 0.5%.

[0031] In the present application, the stabilizer is used by combining high-temperature dispersion and gradual blending. Since the base solvent of the stabilizer is an ionic liquid and hydrorefined white oil, the stabilizer has good high-temperature resistance. The fluidity of the high-viscosity residual oil is improved at high temperature, and a small amount of the stabilizer can achieve good dispersion effect. The stabilizer provided in the present application improves the system stability of the high-viscosity residual oil, and makes the high-viscosity residual oil have good fluidity at a certain temperature through emulsification and viscosity reduction, fully mixes with the light component oil, further reduces the viscosity of the high-viscosity residual oil to make it easy to blend, and at the same time, the low viscosity is conducive to the dispersion and stability of the stabilizer, and improves the effect of the stabilizer on the high-viscosity residual oil.

[0032] Compared with the prior art, the fuel oil stabilizer for blending of high-viscosity residual oil, the preparation and use method thereof provided in the present application have the following advantages:

[0033] 1. The stabilizer of the present application uses ionic liquid as one of the solvents, which has good bidirectional dissolving effect on hydrophilic and oleophilic components, and increases the mixing and dissolving performance between the components. The emulsification and viscosity reduction of high-viscosity residual oil by fatty amine and alkyl phenol polyoxyethylene polyoxypropylene alcohol ether improves the compatibility between high-viscosity residual oil and light component oil. The solubilization and dispersion of high-viscosity residual oil by mono-polyisobutene bis-succinimide maintains the stability of high-viscosity residual oil in blended fuel oil, and prevents coking due to heating of fuel oil during storage and transportation. The stabilizer provided by the present application provides good compatibility, dispersibility, anti-aging property and thermal stability for high-viscosity residual oil blended fuel oil.

[0034] 2. The preparation method of the stabilizer provided by the present application disperses and dissolves the reagent with certain hydrophilicity by using ionic liquid first, and then mixes the reagent with oily medium, which improves the mutual solubility between the reagents during preparation, and prevents uneven mixing and precipitation.

[0035] 3. In the use method of the stabilizer provided by the present application, high-temperature dispersion and gradual blending are used first, the stabilizer is blended with high-viscosity residual oil at high temperature and in a flowing state, the properties of the high-viscosity residual oil are improved and the viscosity is reduced, then the high-viscosity residual oil is mixed with light component oil at normal temperature, the viscosity is further reduced, and the stabilizer is fully dispersed and mixed in the oil product, so as to improve the stability of high-viscosity residual oil in the blending system, and provide an implementation approach for the thermal stability of blended fuel oil. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 The spot imaging diagram of the blended fuel oil prepared for the examples and comparative examples of the present application is shown. DETAILED DESCRIPTION

[0037] The present application is further illustrated by the following examples, but the present application is not limited thereto.

[0038] Example 1

[0039] 10 g of 1-ethyl-3-methylimidazole tetrafluoroborate was heated to 75℃, then 15 g of polyvinylpyrrolidone and 15 g of defoaming agent were added successively and stirred until uniform. Then 8 g of hexanediamine was added at this temperature and stirred again until uniform, to obtain a mixed solution I. 50 g of 7# hydrogenated white oil was heated to 50℃, and 1 g of mono-polyisobutene bis-succinimide and 1 g of alkyl phenol polyoxyethylene polyoxypropylene alcohol ether with alkyl number of 9, addition number ratio of polyoxyethylene to polyoxypropylene of 60:40 and polymerization degree of 45 were added successively under constant stirring, and the mixture was stirred until uniform to obtain a mixed solution II. The mixed solution I and the mixed solution II were stirred at 35℃ for 2 hours, and then filtered to obtain a stabilizer product S1.

[0040] Example 2

[0041] After 25 g of isobutyl tri-butyl quaternary ammonium tetrafluoroborate ionic liquid was heated to 90℃, 25 g of polyvinylpyrrolidone and 12 g of antifoaming agent were added successively and stirred until uniform. Then 3 g of butanediamine was added at this temperature and stirred again until uniform, obtaining mixture I. 34 g of 22# hydrogenated white oil was heated to 55℃, 0.5 g of mono-polyisobutylene disuccinimide and 0.5 g of alkylphenol polyoxyethylene polyoxypropylene alcohol ether with alkyl number of 14, addition number ratio of polyoxyethylene and polyoxypropylene of 70:30 and polymerization degree of 25 were added successively under constant stirring, and after stirring until uniform, mixture II was obtained. After mixture I and mixture II were stirred at 30℃ for 2 hours, the stabilizer product S2 was obtained by filtration.

[0042] Example 3

[0043] After 5 g of 1-isopropyl-3-methyl imidazole bromide was heated to 80℃, 20 g of polyvinylpyrrolidone and 18 g of antifoaming agent were added successively and stirred until uniform. Then 5 g of propylenediamine was added at this temperature and stirred again until uniform, obtaining mixture I. 49 g of 68# hydrogenated white oil was heated to 50℃, 1.2 g of mono-polyisobutylene disuccinimide and 1.8 g of alkylphenol polyoxyethylene polyoxypropylene alcohol ether with alkyl number of 16, addition number ratio of polyoxyethylene and polyoxypropylene of 90:10 and polymerization degree of 60 were added successively under constant stirring, and after stirring until uniform, mixture II was obtained. After mixture I and mixture II were stirred at 30℃ for 2 hours, the stabilizer product S3 was obtained by filtration.

[0044] Comparative Example 1

[0045] The same as the preparation method of Example 1, but 1-ethyl-3-methyl imidazole tetrafluoroborate ionic liquid was not added during the preparation process, obtaining the stabilizer product S4.

[0046] Comparative Example 2

[0047] The same as the preparation method of Example 1, but hexanediamine and alkylphenol polyoxyethylene polyoxypropylene alcohol ether were not added during the preparation process, obtaining the stabilizer product S5.

[0048] Comparative Example 3

[0049] The same as the preparation method of Example 1, but mono-polyisobutylene disuccinimide was not added during the preparation process, obtaining the stabilizer product S6.

[0050] The above six products were subjected to raw material oil addition and stability test.

[0051] The blending fuel oil used in the present embodiment is high viscosity residue oil and light component oil of a certain refinery, and the main physicochemical properties thereof are shown in Table 1. The fuel oil is blended according to the mass percentage of 70% of high viscosity residue oil and 30% of light component oil.

[0052] Table 1 Physicochemical properties of blending fuel oil of a certain refinery

[0053]

[0054] The high viscosity residue oil is heated to 140℃, and after it has good fluidity, 0.03% of the high viscosity residue oil by mass of the above-mentioned six kinds of stabilizers prepared is added respectively. Then it is cooled to 50℃, and 20% of the total mass of the light component oil is added under stirring, and the stirring is continued for 60 min, and the remaining part of the light component oil is added, and the stirring is continued for more than 30 min, to obtain the final blending fuel oil product, which is blending oil 1-6 respectively.

[0055] The stability detection method of the blending fuel oil product is performed according to the evaluation standard of ASTM-D4740. The stability evaluation results are shown in Table 2 and Figure 1 .

[0056] Table 2 Stability evaluation of blending fuel oil

[0057]

[0058] From Table 2 and Figure 1 it can be seen that the stability of the blended fuel oil is better after adding the stabilizer prepared by the method of the present embodiment, and it is further proved that the stabilizer provided by the present embodiment has more excellent blending effect compared with the prior art.

Claims

1. A fuel oil stabilizer for high viscosity residue blending, characterized by, By weight percentage, including: fatty amine 1-15%, mono-polyisobutene bis succinimid 0.1-1.5%, non-ionic surfactant alkyl phenol polyoxyethylene-polyoxypropylene alcohol ether 0.1-2%, alkyl imidazole ionic liquid and / or quaternary ammonium salt ionic liquid 1-30%, polyvinyl pyrrolidone 10-30%, antifoaming agent 10-20%, and the rest is hydrogenated white oil; Wherein, the fatty amine is selected from at least one of ethylenediamine, propylenediamine, butylenediamine or hexylenediamine; The alkyl phenol in the alkyl phenol polyoxyethylene-polyoxypropylene alcohol ether is selected from alkyl with carbon number of 8-18, and the addition number ratio of polyoxyethylene and polyoxypropylene in the block copolymer molecule is 50:50-95:5, and the polymerization degree n of polyoxyethylene group is 10-90; The anion of the alkyl imidazole ionic liquid and / or quaternary ammonium salt ionic liquid is halide ion, tetrafluoroborate ion or hexafluoroborate ion.

2. The fuel oil stabilizer according to claim 1, characterized in that, The hydrogenated white oil is selected from at least one of 5#, 7#, 10#, 15#, 22#, 32#, 46# and 68# white oil.

3. The process for the production of the fuel oil stabilizer as claimed in claim 1 or 2, characterized by, The method comprises the following steps: (1) heating the ionic liquid to a temperature T1, then adding polyvinyl pyrrolidone and antifoaming agent, and stirring uniformly to obtain solution A; (2) dissolving the fatty amine in solution A at the temperature T1, and stirring uniformly to obtain solution B; (3) heating the hydrogenated white oil to a temperature T2 and continuously stirring, then adding mono-polyisobutene bis succinimid, adding alkyl phenol polyoxyethylene-polyoxypropylene alcohol ether after uniform mixing, and stirring uniformly at the temperature T2 to obtain mixed solution C; (4) mixing solution B and solution C at a temperature T3, and stirring for 1.5-3 hours; (5) after the stirring is completed, filtering the solution to obtain the fuel oil stabilizer.

4. The production method according to claim 3, characterized by, T1 is 60-100℃, T2 is 40-60℃, and T3 is 25-40℃.

5. The fuel oil stabilizer of claim 1 or 2 is applied in blending of high-viscosity residual oil.

6. Use according to claim 5, characterized in that, The method comprises the following steps: (a) heating the high-viscosity residual oil to t1, then adding the stabilizer after the high-viscosity residual oil has good fluidity, and stirring uniformly to obtain component oil M; (b) reducing the temperature of the component oil M to t2, then adding a part of light component oil under stirring, continuously stirring for 30-90 min, and obtaining component oil N which is fully emulsified and reduced in viscosity; (c) fully mixing the remaining part of light component oil in the component oil N at a temperature t3, and stirring for more than 30 min to obtain blended fuel oil product.

7. Use according to claim 6, characterized in that, t1 is 80-180℃, t2 is 50-80℃, and t3 is room temperature-50℃.

Images