CN104785297A - Catalyst for preparing antiwear agent of aviation fuel - Google Patents
Catalyst for preparing antiwear agent of aviation fuel Download PDFInfo
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- CN104785297A CN104785297A CN201510134538.6A CN201510134538A CN104785297A CN 104785297 A CN104785297 A CN 104785297A CN 201510134538 A CN201510134538 A CN 201510134538A CN 104785297 A CN104785297 A CN 104785297A
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- ionic liquid
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Abstract
The invention relates to a catalyst for preparing an antiwear agent of aviation fuel. The catalyst comprises ionic liquid I and ionic liquid II having the following structural formulae as shown in the specification.
Description
Technical field
The present invention relates to
a kind of catalyst for the preparation of aviation fuel antiwear additive, especially a kind of ionic liquid.
Background technology
At present, the antiwear additive added in domestic air mail fuel is the active principle of T1602, T1602 is aphthenic acids, and aphthenic acids is the component wishing in jet fuel processing to remove, and rejoin aphthenic acids the acidity of aviation fuel can be caused to increase, the corrosivity of jet fuel also can be caused to increase.And the colourity of T1602 additive is comparatively dark, affects the colour index of aviation fuel, in addition, the unstable product quality of T1602.
Aviation fuel mainly adopts acid-alkali refining, hydrofinishing or hydrocracking in process of production, natural wear-resistant composition in cut is removed, cause aviation fuel abrasion resistance to reduce, therefore must add antiwear additive in aviation fuel, prevent the heavy wear of fuel system.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention proposes
a kind of catalyst for the preparation of aviation fuel antiwear additive, use this catalyst can synthesize a kind of antiwear additive of aviation fuel of excellent performance, be particularly useful for the antiwear additive of jet fuel, and the antiwear additive of this catalyst of unexpected use synthesis, greatly improve the corrosive nature of former cycloalkanes acid type additive.
A kind of antiwear additive of aviation fuel, comprise C36 unrighted acid dimer, this C36 unrighted acid dimer comprises: the compound more than 65% shown in general formula (1), compound 25-30% shown in general formula (2), compound shown in general formula (3) lower than 10%, in mass.
Above-mentioned C36 unrighted acid dimer prepares as follows:
(A) preparation of fatty acid mixed: comprise vegetable oil to mix with excessive aqueous slkali and appropriate ethanol and carry out saponification and slough glycerine, generate soap, soap is through being acidified to pH=2 ~ 3, adopt petroleum ether extraction oil phase, oil phase is after washing, anhydrous sodium sulfate drying, adopt rotary evaporation removing benzinum, after vacuum drying fatty acid mixed;
(B1) synthesis of C36 unrighted acid dimer, comprises the steps:
(1) be placed in autoclave using the fatty acid mixed of linoleic acid or step (A) gained as raw material, add the catalyst of 9-15% and the auxiliary agent of 0.5-1.5% again, based on the quality meter of linoleic acid or above-mentioned fatty acid mixed, install autoclave, and check air-tightness, wherein catalyst is treated earth, auxiliary agent is lithium carbonate, the preferred 10-13% of use amount of catalyst, more preferably 12%, the preferred 0.8-1.2% of use amount of auxiliary agent, more preferably 1.0%;
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen is to 2.0MPa, closes autoclave intake valve;
(3) under the condition stirred, be heated to reaction temperature 230-240 DEG C, when arriving reaction temperature, start timing, as reacting zero point;
(4) react after within 5-6 hour, terminating, stop heating, autoclave kettle is placed in cold water, makes kettle drop to room temperature rapidly, drives still, and pour out product;
(5) crude product equal-volume benzinum dilution, and add excessive hydrochloric acid and be acidified to pH=2 ~ 3;
(6) after acidifying, mixture is carried out centrifugation, removing catalyst and solid impurity;
(7) supernatant liquor deionized water is washed till neutrality, separatory, upper oil phase anhydrous sodium sulfate drying, hold over night, crosses and filters anhydrous sodium sulfate;
(8) rotary evaporation in vacuo removing benzinum, remove unreacted monomer acids finally by decompression distillation, the condition of decompression distillation is: gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtains refined products.
Step B1 can adopt step B2 to replace, and step B2 comprises the steps:
(1) be placed in autoclave using the fatty acid mixed of linoleic acid or step (A) gained as raw material, add the ionic liquid of 9-15% again as catalyst, based on the quality meter of linoleic acid or above-mentioned fatty acid mixed, install autoclave, and check air-tightness, the preferred 10-13% of use amount of catalyst, more preferably 12%, ionic liquid is ionic liquid I or the ionic liquid II with following structural formula
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen is to 2.0MPa, closes autoclave intake valve;
(3) under the condition stirred, be heated to reaction temperature 230-240 DEG C, when arriving reaction temperature, start timing, as reacting zero point;
(4) react after within 5-6 hour, terminating, stop heating, autoclave kettle is placed in cold water, makes kettle drop to room temperature rapidly, drives still, and pour out product;
(5) crude product equal-volume benzinum dilution, and add excessive hydrochloric acid and be acidified to pH=2 ~ 3;
(6) after acidifying, supernatant liquor deionized water is washed till neutrality, separatory, upper oil phase anhydrous sodium sulfate drying, hold over night, and cross and filter anhydrous sodium sulfate, the ionic liquid of lower floor is recyclable to be recycled;
(7) rotary evaporation in vacuo removing benzinum, remove unreacted monomer acids finally by decompression distillation, the condition of decompression distillation is: gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtains refined products.
The synthesis of ionic liquid I:
Ionic liquid I specifically adopts following preparation method:
(1) in conical flask, trimethylamine solution is mixed with PS etc. mole, stirring reaction 24h at 60 DEG C;
(2), after reaction terminates, rotary distillation, except anhydrating, obtains white solid;
(3) by re-crystallizing in ethyl acetate, suction filtration, and wash three times;
(4) vacuum drying (80 DEG C) 4h obtains the solid inner salt of white;
(5) with the water-soluble solution inner salt of 3 times of quality;
(6) drip the hcl acidifying that equimolar mass concentration is 37%, dropwise, be warming up to 80 DEG C, stirring reaction 3h.
(7) rotary distillation is except anhydrating, and vacuum drying (80 DEG C) 4h, obtains light yellow viscous liquid, i.e. acidifying inner salt;
(8) get a certain amount of acidifying inner salt, the zinc chloride being 1:2 with mol ratio mixes, and under nitrogen protection, is warming up to 100 DEG C, is stirred to solid and all dissolves;
(9) vacuum drying (80 DEG C) 8h, obtains thick ionic liquid I.
The synthesis of ionic liquid II:
The concrete synthesis step of ionic liquid II is as follows:
(1) a certain amount of PS being dissolved in its mass number is in the ethyl acetate of 5 ~ 10 times, is warming up to 40 ~ 60 DEG C, drips equimolar N-methylimidazole.Dropwise, insulation reaction 3 ~ 5h;
(2), after reaction terminates, suction filtration, obtains white filter cake, and filter cake ethyl acetate washs three times;
(3) vacuum drying (100 DEG C) 2h obtains white solid inner salt 3-(1-methylimidazole-3-alkyl)-propyl sulfonic acid salt (mim-PS);
(4) get a certain amount of inner salt mim-PS, being dissolved in its mass number is in the deionized water of 2 ~ 4 times;
(5) drip the hydrochloric acid that equimolar mass concentration is 37%, acidifying is complete, is warming up to 70 ~ 90 DEG C, stirring reaction 2 ~ 3h;
(6) rotary distillation is except anhydrating, and vacuum drying (80 DEG C) 4h, obtains light yellow viscous liquid, i.e. acidifying inner salt chlorination 1-(3-sulfonic acid)-propyl group-3-methylimidazole salt [HO
3s-(CH
2)
3-mim] Cl;
(7) get a certain amount of acidifying inner salt, the zinc chloride being 1:2 with mol ratio mixes, and under nitrogen protection, is warming up to 90 ~ 110 DEG C, is stirred to solid and all dissolves;
(8) vacuum drying (80 DEG C) 8h, obtains thick ionic liquid II.
Description
accompanying drawing
fig. 1that the impact of number of times on C36 unrighted acid dimer (KM3) yield reused by catalyst
embodiment
Embodiment 1
Prepare fatty acid mixed:
(1) 100g sunflower oil is accurately taken in 250mL there-necked flask.
(2) 40g KOH is added, 95% ethanolic solution of 80g deionized water (or 40ml 50%KOH solution) and 160ml.
(3) under 90 DEG C of glycerol bath conditions, stirring and refluxing saponification 2h, obtains saponification liquor (saponification liquor that takes a morsel is water-soluble, if leave standstill without oil reservoir, then saponification is complete).
(4) treat that saponification liquor is cooled to room temperature, add watery hydrochloric acid and be acidified to pH=2 ~ 3, with a small amount of petroleum ether extraction oil phase.
(5) acidifying is complete, is washed till neutrality by deionized water, separatory.Upper oil phase anhydrous sodium sulfate drying, hold over night.
(6) excessively anhydrous sodium sulfate is filtered.
(7) rotary evaporation in vacuo removing benzinum, vacuum drying, obtains fatty acid mixed.
Embodiment 2
The synthesis of C36 unrighted acid dimer:
(1) be placed in autoclave as raw material using the fatty acid mixed of embodiment 1 gained, then add the catalyst of 12% and the auxiliary agent of 1%, based on the quality meter of above-mentioned fatty acid mixed, install autoclave, and check air-tightness, wherein catalyst is treated earth, and auxiliary agent is lithium carbonate;
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen is to 2.0MPa, closes autoclave intake valve;
(3) under the condition stirred, be heated to reaction temperature 240 DEG C, when arriving reaction temperature, start timing, as reacting zero point;
(4) react after within 6 hours, terminating, stop heating, autoclave kettle is placed in cold water, makes kettle drop to room temperature rapidly, drives still, and pour out product;
(5) crude product equal-volume benzinum dilution, and add excessive hydrochloric acid and be acidified to pH=2 ~ 3;
(6) after acidifying, mixture is carried out centrifugation, removing catalyst and solid impurity;
(7) supernatant liquor deionized water is washed till neutrality, separatory, upper oil phase anhydrous sodium sulfate drying, hold over night, crosses and filters anhydrous sodium sulfate;
(8) rotary evaporation in vacuo removing benzinum, remove unreacted monomer acids finally by decompression distillation, the condition of decompression distillation is: gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtain refined products, the yield of C36 unrighted acid dimer is 67.6%.
Embodiment 3
The synthesis of C36 unrighted acid dimer:
(1) be placed in autoclave as raw material using linoleic acid, then add the catalyst of 12% and the auxiliary agent of 1%, based on above-mentioned linoleic quality meter, install autoclave, and check air-tightness, wherein catalyst is treated earth, and auxiliary agent is lithium carbonate;
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen is to 2.0MPa, closes autoclave intake valve;
(3) under the condition stirred, be heated to reaction temperature 230 DEG C, when arriving reaction temperature, start timing, as reacting zero point;
(4) react after within 6 hours, terminating, stop heating, autoclave kettle is placed in cold water, makes kettle drop to room temperature rapidly, drives still, and pour out product;
(5) crude product equal-volume benzinum dilution, and add excessive hydrochloric acid and be acidified to pH=2 ~ 3;
(6) after acidifying, mixture is carried out centrifugation, removing catalyst and solid impurity;
(7) supernatant liquor deionized water is washed till neutrality, separatory, upper oil phase anhydrous sodium sulfate drying, hold over night, crosses and filters anhydrous sodium sulfate;
(8) rotary evaporation in vacuo removing benzinum, remove unreacted monomer acids finally by decompression distillation, the condition of decompression distillation is: gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtain refined products, the yield of C36 unrighted acid dimer is 88.7%.
Embodiment 4
The synthesis of C36 unrighted acid dimer:
(1) be placed in autoclave using the fatty acid mixed of embodiment 1 gained as raw material, then the ionic liquid I adding 10% is as catalyst, based on the quality meter of above-mentioned fatty acid mixed, installs autoclave, and checks air-tightness
(2) purge autoclave three times with nitrogen, discharge the air in autoclave, then inflated with nitrogen is to 2.0MPa, closes autoclave intake valve;
(3) under the condition stirred, be heated to reaction temperature 230 DEG C, when arriving reaction temperature, start timing, as reacting zero point;
(4) react after within 5 hours, terminating, stop heating, autoclave kettle is placed in cold water, makes kettle drop to room temperature rapidly, drives still, and pour out product;
(5) crude product equal-volume benzinum dilution, and add excessive hydrochloric acid and be acidified to pH=2 ~ 3;
(6) after acidifying, supernatant liquor deionized water is washed till neutrality, separatory, upper oil phase anhydrous sodium sulfate drying, hold over night, and cross and filter anhydrous sodium sulfate, the ionic liquid of lower floor is recyclable to be recycled;
(7) rotary evaporation in vacuo removing benzinum, remove unreacted monomer acids finally by decompression distillation, the condition of decompression distillation is: gas phase temperature is 240 DEG C, and residual voltage is 133Pa (1mmHg), obtain refined products, the yield of C36 unrighted acid dimer is 63.3%.
Embodiment 5
The synthesis of C36 unrighted acid dimer:
Using ionic liquid II as catalyst, other conditions are all identical with embodiment 5, prepare refined products, and the yield of C36 unrighted acid dimer is 64.9%.
Embodiment 6
The synthesis of C36 unrighted acid dimer:
Take linoleic acid as raw material, other conditions are identical with embodiment 5, obtain refined products, and the yield of C36 unrighted acid dimer is 86.5%.
Embodiment 8
The synthesis of C36 unrighted acid dimer:
Take linoleic acid as raw material, using ionic liquid II as catalyst, other conditions are all identical with embodiment 5, prepare refined products, and the yield of C36 unrighted acid dimer is 87.4%.
Embodiment 9
When identical with the reaction condition of embodiment 4, investigated ion I liquid and reused the impact of number of times on C36 unrighted acid dimer yield, result as
accompanying drawing 1shown in:
By
accompanying drawing 1can find out, after ionic liquid I reuses 5 times, the yield kept stable of C36 unrighted acid dimer, illustrates that ionic liquid has good repeat performance.This can explain from two aspects: (1) ionic liquid
acid centre is positioned at the alkyl sulfonic acid that covalent bond is connected on its cation, Lewis acid centre be then to water and
anion [the Zn that acidic materials are stable
2cl
5]
-, therefore the acid centre of ionic liquid not easily runs off; (2) ZnCl
2introducing make the viscosity of ionic liquid and proportion all comparatively large, be conducive to it and be separated with reactant mixture, make the loss of ionic liquid in separation process very little.
Wear-resistant and corrosion resistant test data: unsaturated acids, because the existence of double bond, easier in metal surface formation adsorbed film, therefore abrasion resistance is better than linear saturated fatty acids.The corrosivity of aphthenic acids is larger than dimeric dibasic acid.
This agent adds in No. 3 jet fuels of hydrogenation technique production should meet following index (addition 15 ~ 23mg/L):
1. lubricity: wear scar diameter (WSD) is less than 0.65mm.(SH/T 0687) representative value 0.59mm
2. water separation index: MSEP >=75.(SH/T 0616) representative value 85 ~ 95
3. copper corrosion: be less than or equal to 1 grade (GB/T5096)
Claims (5)
1., for the preparation of a catalyst for aviation fuel antiwear additive, this catalyst is ionic liquid I or the ionic liquid II with following structural formula,
2. catalyst according to claim 1, is characterized in that: described ionic liquid I synthesizes following process:
3. catalyst according to claim 1, is characterized in that: described ionic liquid I specifically adopts following preparation method:
(1) in conical flask, trimethylamine solution is mixed with PS etc. mole, stirring reaction 24h at 60 DEG C;
(2), after reaction terminates, rotary distillation, except anhydrating, obtains white solid;
(3) by re-crystallizing in ethyl acetate, suction filtration, and wash three times;
(4) vacuum drying (80 DEG C) 4h obtains the solid inner salt of white;
(5) with the water-soluble solution inner salt of 3 times of quality;
(6) drip the hcl acidifying that equimolar mass concentration is 37%, dropwise, be warming up to 80 DEG C, stirring reaction 3h.
(7) rotary distillation is except anhydrating, and vacuum drying (80 DEG C) 4h, obtains light yellow viscous liquid, i.e. acidifying inner salt;
(8) get a certain amount of acidifying inner salt, the zinc chloride being 1:2 with mol ratio mixes, and under nitrogen protection, is warming up to 100 DEG C, is stirred to solid and all dissolves;
(9) 80 DEG C of vacuum drying 8h, obtain thick ionic liquid I.
4. catalyst according to claim 1, is characterized in that: described ionic liquid II synthesizes following process:
5. catalyst according to claim 1, is characterized in that: the concrete synthesis step of described ionic liquid II is as follows:
(1) a certain amount of PS being dissolved in its mass number is in the ethyl acetate of 5 ~ 16 times, is warming up to 40 ~ 60 DEG C, drips equimolar N-methylimidazole.Dropwise, insulation reaction 3 ~ 5h;
(2), after reaction terminates, suction filtration, obtains white filter cake, and filter cake ethyl acetate washs three times;
(3) vacuum drying (100 DEG C) 2h obtains white solid inner salt 3-(1-methylimidazole-3-alkyl)-propyl sulfonic acid salt (mim-PS);
(4) get a certain amount of inner salt mim-PS, being dissolved in its mass number is in the deionized water of 2 ~ 4 times;
(5) drip the hydrochloric acid that equimolar mass concentration is 37%, acidifying is complete, is warming up to 70 ~ 90 DEG C, stirring reaction 2 ~ 3h;
(6) rotary distillation is except anhydrating, and 80 DEG C of vacuum drying 4h, obtain light yellow viscous liquid, i.e. acidifying inner salt chlorination 1-(3-sulfonic acid)-propyl group-3-methylimidazole salt [HO
3s-(CH
2)
3-mim] Cl;
(7) get a certain amount of acidifying inner salt, the zinc chloride being 1:2 with mol ratio mixes, and under nitrogen protection, is warming up to 90 ~ 110 DEG C, is stirred to solid and all dissolves;
(8) 80 DEG C of vacuum drying 8h, obtain thick ionic liquid II.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348448A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of ion liquid having B acid center and L acid center |
| JP2009224097A (en) * | 2008-03-14 | 2009-10-01 | Panasonic Corp | Nonaqueous electrolyte secondary battery |
| CN101613273A (en) * | 2009-07-25 | 2009-12-30 | 青岛科技大学 | A kind of preparation method of dimeric acid methyl ester |
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2015
- 2015-03-25 CN CN201510134538.6A patent/CN104785297B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009224097A (en) * | 2008-03-14 | 2009-10-01 | Panasonic Corp | Nonaqueous electrolyte secondary battery |
| CN101348448A (en) * | 2008-09-04 | 2009-01-21 | 华东师范大学 | Preparation of ion liquid having B acid center and L acid center |
| CN101613273A (en) * | 2009-07-25 | 2009-12-30 | 青岛科技大学 | A kind of preparation method of dimeric acid methyl ester |
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