CN101691508B - Low temperature diesel flow improver and preparation method thereof - Google Patents
Low temperature diesel flow improver and preparation method thereof Download PDFInfo
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- CN101691508B CN101691508B CN 200910019449 CN200910019449A CN101691508B CN 101691508 B CN101691508 B CN 101691508B CN 200910019449 CN200910019449 CN 200910019449 CN 200910019449 A CN200910019449 A CN 200910019449A CN 101691508 B CN101691508 B CN 101691508B
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- diesel oil
- vinylpyridine
- vinyl
- tetrapolymer
- ethene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000002283 diesel fuel Substances 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 229920006029 tetra-polymer Polymers 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 7
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical group NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000009833 condensation Methods 0.000 abstract description 6
- 230000005494 condensation Effects 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- -1 cyclohexyl carbimide Chemical compound 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The invention discloses a low temperature diesel flow improver which comprises 90-98wt% of ethylene-N-octylacrylamide-vinyl acetate-2-vinylpyridine quadripolymers and 2-10wt% amine substances. The invention also discloses a preparation method of the flow improver, comprising the following steps: first dissolving the ethylene, N-octylacrylamide, vinyl acetate and 2-vinylpyridine into cyclohexane under the protection of nitrogen, then adding an initiator to react for 1-2h under the temperature of 80-150 DEG C and the pressure of 5-10MPa, removing solvents and washing to obtain the quadripolymers; and then proportionally mixing the amine substances with the quadripolymers evenly, thus obtaining the low temperature diesel flow improver of the invention. The low temperature diesel flow improver has good effect on stably dispersing microcrystallines, can more effectively lower the condensation point and the cold filter point of the diesel and improve the sensitivity to the diesel from different sources.
Description
Technical field
The present invention relates to a kind of diesel oil at low-temperature fluidity improver and preparation method thereof; Particularly, relate to diesel oil at low-temperature fluidity improver that a kind of ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine tetrapolymer and amine substance form and preparation method thereof.
Background technology
The diesel oil at low-temperature fluidity improver is a diesel pour inhibitor, is a kind of additive commonly used in the present diesel production.Pour point depressant has destruction or changes the function of wax crystallization, can reduce the cold filter clogging temperature and the condensation point of diesel oil.Use ethylene-vinyl acetate analog copolymer product more generally in China at present, common diesel oil at low-temperature fluidity improver can both improve the condensation point of diesel oil, but to the DeGrain that improves of cold worry point, and bad to the susceptibility of part diesel oil.Most of low wax diesel oil has susceptibility preferably to above-mentioned low temperature flow promoter; But it can not satisfy the service index requirement of diesel oil fully; As in 0# diesel oil, add commercially available low temperature flow promoter T1804 result of use with-10# diesel oil effect is suitable, but T1804 to high wax diesel oil to fall the cold filter clogging temperature effect relatively poor.
Summary of the invention
In order to address the above problem; The present invention prepares and has synthesized ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine tetrapolymer; And add a certain amount of amine substance, and can effectively reduce the condensation point and the cold worry point of diesel oil, improve susceptibility to different sources diesel oil.
Diesel oil at low-temperature fluidity improver of the present invention is made up of the ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine tetrapolymer of 90-98wt% and the amine substance of 2-10wt%, and the chemical structural formula of described tetrapolymer is:
K, L, m, the n integer of 5-45 of respectively doing for oneself wherein;
Ethene in the diesel oil at low-temperature fluidity improver of the present invention-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine tetrapolymer; Its nonpolar segment is by forming with the long-chain alkane of normal paraffin structure similar, have bigger solid and cover crystallite-cladded ability, when long-chain alkane form with normal paraffin closely near the time; The eutectic effect takes place; At this moment the nonpolar segment of the multipolymer fixed effect of weighing anchor is used for interfacial adsorption, has effectively prevented further growing up of crystal grain.
Amine substance in the diesel oil at low-temperature fluidity improver of the present invention is aminopropyl morpholine, diamino-pyridine or urotropin.Amine substance can and the non-polar group of multipolymer is collaborative plays the stable dispersion effect between the crystallite, change phase interface state and flow-pattern, reduced the Intermolecular Forces of wax with oil, effectively reduced the condensation point and the cold worry point of diesel oil more.
The preparation method of diesel oil at low-temperature fluidity improver of the present invention comprises the steps:
(1) with ethene, N-octyl acrylamide, vinyl-acetic ester, 2-vinylpyridine polymerization single polymerization monomer under nitrogen protection, be dissolved in mix in the cyclohexane solvent after; Left standstill 0.5-1 hour; Add composite initiator N; N'-two cyclohexyl carbimide and ethylaluminium dichlorides behind the reaction 1-2h, add the mixing solutions of the second alcohol and water that contains NaOH under 80-150 ℃, 5-10Mpa pressure; Remove solvent and unreacted polymerization single polymerization monomer, washing and drying obtains ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine tetrapolymer;
(2) tetrapolymer that takes by weighing amine substance and above-mentioned steps (1) gained in proportion 45-80 ℃ of following thorough mixing even diesel oil at low-temperature fluidity improver of the present invention.
The mol ratio of the ethene described in above-mentioned preparing method's step (1), N-octyl acrylamide, vinyl-acetic ester, 2-vinylpyridine is 1:1:1:1; Described composite initiator amount is the 5-10% of polymerization single polymerization monomer gross weight; Hexanaphthene volume (ml): polymerization single polymerization monomer gross weight (g)=2-4, the amount of the mixing solutions of second alcohol and water are the 5-10% of polymerization single polymerization monomer gross weight.
Described composite initiator N, the weight ratio of N'-two cyclohexyl carbimides and ethylaluminium dichloride is 0.5-1.5; In the mixing solutions of the described second alcohol and water that contains NaOH, the volume ratio of second alcohol and water is 1, and the NaOH amount is the 0.5-1% of mixing solutions weight.
N-octyl acrylamide described in the above-mentioned preparation process (1) can make through following method: 24g triethylamine and 28g NSC 9824 are dissolved in the 200ml THF; Under 0-5 ℃, feed nitrogen, in 2.5h, drip the tetrahydrofuran solution 200ml that contains the 16g acrylic amide, drip the complete 10 ℃ of reaction 2-4h that are warming up to; Remove solvent and get light yellow oily liquid; Again in-25 ℃ down with acetone recrystallization 2 times, vacuum (vacuum tightness-0.090--0.095Mpa) drying, promptly get.
Diesel oil at low-temperature fluidity improver of the present invention, three-dimensional parcel level of coverage is big, has the good stable dispersion effect to crystallite, can effectively reduce the condensation point and the cold worry point of diesel oil more, has improved the susceptibility to different sources diesel oil.
Embodiment
Embodiment 1
28g (1mol) ethene, 183g (1mol) N-octyl acrylamide, 86g (1mol) vinyl-acetic ester, 105g (1mol) 2-vinylpyridine polymerization single polymerization monomer are dissolved under nitrogen protection mix in the cyclohexane solvent of 1200ml after; Leave standstill 30min; Add 12g; N, the composite initiator that N'-two cyclohexyl carbimides and 24g ethylaluminium dichloride are formed is after reacting 2h under 100 ℃ the temperature, 8Mpa pressure under; The mixing solutions that adding 40g contains the ethanol/water (V/V=1) of 1wt%NaOH stops polymerization; After polymerisate removed solvent and unreacted polymerization single polymerization monomer, the washing purifying was dry, obtains tetrapolymer ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine.With gained tetrapolymer and aminopropyl morpholine according to weight ratio thorough mixing under 60 ℃ of conditions of 49:1 even a kind of diesel oil at low-temperature fluidity improver A of the present invention.
Embodiment 2
After 28g (1mol) ethene, 183g (1mol) N-octyl acrylamide, 86g (1mol) vinyl-acetic ester, 105g (1mol) 2-vinylpyridine polymerization single polymerization monomer be dissolved under nitrogen protection and mix in the 1600ml cyclohexane solvent; Leave standstill 60min; The N that adds 24g; The composite initiator that N'-two cyclohexyl carbimides and 16g ethylaluminium dichloride are formed; Behind reaction 1h under 150 ℃ the temperature, under the 10Mpa pressure, the mixing solutions that adds the ethanol/water that contains 0.5wt%NaOH (V/V=1) of 40g stops polymerization, and polymerisate is after removing solvent and unreacted polymerization single polymerization monomer; The washing purifying is dry, obtains tetrapolymer ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine.With gained tetrapolymer and urotropin according to weight ratio thorough mixing under 45 ℃ of conditions of 9:1 even a kind of diesel oil at low-temperature fluidity improver B of the present invention.
Embodiment 3
After 28g (1mol) ethene, 183g (1mol) N-octyl acrylamide, 86g (1mol) vinyl-acetic ester, 105g (1mol) 2-vinylpyridine polymerization single polymerization monomer be dissolved under nitrogen protection and mix in the 850ml cyclohexane solvent; Leave standstill 60min; The N that adds 10g; The composite initiator that N'-two cyclohexyl carbimides and 15g ethylaluminium dichloride are formed; Behind reaction 1h under 150 ℃ the temperature, under the 10Mpa pressure, add the mixing solutions termination polymerization that 25g contains the ethanol/water (V/V=1) of 1wt%NaOH, polymerisate is after removing solvent and unreacted polymerization single polymerization monomer; The washing purifying is dry, obtains tetrapolymer ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine.With gained tetrapolymer and diamino-pyridine according to weight ratio thorough mixing under 45 ℃ of conditions of 9:1 even a kind of diesel oil at low-temperature fluidity improver C of the present invention.
Respectively according to 300ppm, 500ppm, the addition of 700ppm add in 0# and the 10# diesel oil in the commercially available different places of production and test test-results such as table 1 with the prepared diesel oil at low-temperature fluidity improver of embodiment 1-3 A-C
Table 1: diesel oil at low-temperature fluidity improver of the present invention is to the test effect of 0# diesel oil
According to table 1; With the diesel oil total amount is benchmark; Addition according to 700ppm is added into diesel oil at low-temperature fluidity improver of the present invention in the 0# diesel oil of different sources, and the highest reduction of cold filter clogging temperature reaches 7 ℃ (Lip river refining 0#), diesel oil at low-temperature fluidity improver of the present invention is added in the 10# diesel oil of different sources according to the addition of 700ppm; All can reduce the cold filter clogging temperature of 10# diesel oil, the highest reduction reaches 5 ℃ (huge port 10#).
Claims (4)
1. a diesel oil at low-temperature fluidity improver is characterized in that being made up of the ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine tetrapolymer of 90-98wt% and the amine substance of 2-10wt%, and the chemical structural formula of described tetrapolymer is:
Wherein k, L, m, n respectively are the integer of 5-45; Described amine substance is aminopropyl morpholine, diamino-pyridine or urotropin.
2. a method for preparing the described diesel oil at low-temperature fluidity improver of claim 1 is characterized in that comprising the steps:
(1) ethene, N-octyl acrylamide, vinyl-acetic ester, four kinds of polymerization single polymerization monomers of 2-vinylpyridine are dissolved under nitrogen protection and mix in the hexanaphthene after; Left standstill 0.5-1 hour; Add composite initiator N; N '-dicyclohexyl carbimide and ethylaluminium dichloride behind the reaction 1-2h, adds the mixing solutions of the second alcohol and water that contains NaOH under 80-150 ℃, 5-10Mpa pressure; Remove solvent and unreacted polymerization single polymerization monomer, washing and drying obtains ethene-N-octyl acrylamide-vinyl-acetic ester-2-vinylpyridine tetrapolymer;
(2) tetrapolymer that takes by weighing amine substance and above-mentioned steps (1) gained in proportion evenly promptly gets diesel oil at low-temperature fluidity improver of the present invention at 45-80 ℃ of following thorough mixing;
The mol ratio of the ethene described in the step (1), N-octyl acrylamide, vinyl-acetic ester, 2-vinylpyridine is 1: 1: 1: 1; Described composite initiator amount is the 5-10% of polymerization single polymerization monomer gross weight; Hexanaphthene volume (ml): polymerization single polymerization monomer gross weight (g)=2-4; The amount of the mixing solutions of second alcohol and water is the 5-10% of polymerization single polymerization monomer gross weight.
3. preparation method according to claim 2 is characterized in that described composite initiator N, and the weight ratio of N '-dicyclohexyl carbimide and ethylaluminium dichloride is 0.5-1.5.
4. preparation method according to claim 2 is characterized in that the volume ratio of second alcohol and water is 1 in the mixing solutions of second alcohol and water of the described NaOH of containing, and NaOH is the 0.5-1% of mixing solutions weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910019449 CN101691508B (en) | 2009-10-20 | 2009-10-20 | Low temperature diesel flow improver and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910019449 CN101691508B (en) | 2009-10-20 | 2009-10-20 | Low temperature diesel flow improver and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101691508A CN101691508A (en) | 2010-04-07 |
| CN101691508B true CN101691508B (en) | 2012-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200910019449 Expired - Fee Related CN101691508B (en) | 2009-10-20 | 2009-10-20 | Low temperature diesel flow improver and preparation method thereof |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3085384A1 (en) * | 2018-08-28 | 2020-03-06 | Total Marketing Services | USE OF SPECIFIC COPOLYMERS FOR IMPROVING THE COLD PROPERTIES OF FUELS OR FUELS |
| FR3085383A1 (en) * | 2018-08-28 | 2020-03-06 | Total Marketing Services | ADDITIVE COMPOSITION COMPRISING AT LEAST ONE COPOLYMER, A COLD FLUIDIFYING ADDITIVE AND ANTI-SEDIMENTATION ADDITIVE |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772574A (en) * | 2013-12-25 | 2014-05-07 | 济南开发区星火科学技术研究院 | Preparation method of diesel oil pour point depressant containing styrene-fumaric acid copolymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287154A (en) * | 2000-06-13 | 2001-03-14 | 石油大学(华东) | Diesel oil modifier for improving low-temperature flowability |
| CN1362498A (en) * | 2001-11-17 | 2002-08-07 | 中国石油化工集团公司 | Low temperature flowing additive for diesel oil |
-
2009
- 2009-10-20 CN CN 200910019449 patent/CN101691508B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287154A (en) * | 2000-06-13 | 2001-03-14 | 石油大学(华东) | Diesel oil modifier for improving low-temperature flowability |
| CN1362498A (en) * | 2001-11-17 | 2002-08-07 | 中国石油化工集团公司 | Low temperature flowing additive for diesel oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3085384A1 (en) * | 2018-08-28 | 2020-03-06 | Total Marketing Services | USE OF SPECIFIC COPOLYMERS FOR IMPROVING THE COLD PROPERTIES OF FUELS OR FUELS |
| FR3085383A1 (en) * | 2018-08-28 | 2020-03-06 | Total Marketing Services | ADDITIVE COMPOSITION COMPRISING AT LEAST ONE COPOLYMER, A COLD FLUIDIFYING ADDITIVE AND ANTI-SEDIMENTATION ADDITIVE |
| EP3844250B1 (en) * | 2018-08-28 | 2024-04-03 | TotalEnergies OneTech | Use of specific copolymers for improving the cold properties of fuels or combustibles |
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| CN101691508A (en) | 2010-04-07 |
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