CN1035883C - Additive for stability of diesel oil - Google Patents

Additive for stability of diesel oil Download PDF

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Publication number
CN1035883C
CN1035883C CN93104289A CN93104289A CN1035883C CN 1035883 C CN1035883 C CN 1035883C CN 93104289 A CN93104289 A CN 93104289A CN 93104289 A CN93104289 A CN 93104289A CN 1035883 C CN1035883 C CN 1035883C
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China
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diesel oil
oil
additive
catalytic cracking
stability
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CN93104289A
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CN1094084A (en
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崔华
刘继峰
张欣
赵来甫
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00Engines characterised by air compression and subsequent fuel addition
    • F02B3/06Engines characterised by air compression and subsequent fuel addition with compression ignition

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  • Lubricants (AREA)

Abstract

The present invention relates to an additive for improving stability of diesel oil, which is prepared from tertiary amine and shielding phenol. The additive has the advantages of easily available raw materials and simple preparing process. The additive can be used for improving storage stability of straight-run diesel oil and secondary processing diesel oil.

Description

Additive for stability of diesel oil
The present invention relates to a kind of additive for stability of diesel oil, or rather, relate to the composite additive that combines by two kinds of compounds, be used to improve the stability in storage of solar oil.
Along with crude oil becomes heavy day by day, the development of deep processing technology, the diesel oil stability problem is more and more outstanding, and particularly secondary processing diesel oil such as catalytic cracking diesel oil stability are poorer, and in storage process, color deepens very soon, and colloid and insolubles increase sharply.Insolubles and colloid that diesel oil forms directly influence its use properties, cause engine filters to stop up, and prime the fuel system can not normal fuel injection, influence oil atomizing, causes incomplete combustion, even form too much carbon deposit in engine, makes the nozzle obstruction.Therefore, for solving the problem of diesel oil fuel stability, several different methods occurred, a kind of method wherein adds additive exactly in diesel oil, and is rotten to suppress it, improves its stability.Propyl group urea composite additive with the second month in a season or uncle's aliphatic amide and the replacement of N-alkyl is proposed among the USP3139330, can suppress or reduce the sedimental formation of ignition internal combustion engine inlet system, but the ring urea component need just can make in this additive in higher temperature of reaction and long reaction times; USP4501595 introduces earlier by tetraethylenepentamine and Paraformaldehyde 96,2,6-di-tert-butylphenol generation condensation reaction, obtain phenol-aldehyde-amine condensation product again with contain the Succinic anhydried generation condensation reaction that polyisobutene replaces, final product can improve the diesel oil stability in storage, but this additive needs plurality of raw materials, and will make through secondary reaction; USP4648885 introduces a kind of with N-(2-aminoethyl) piperazine, triethylenetetramine and N, the mixture of N-diethyl hydroxylamine is an additive, can stop diesel colour to deepen formation with particulate matter, but this composite additive only improves the stability in storage of straight distillation light diesel oil, range of application is narrower.
The purpose of this invention is to provide a kind of raw material and be easy to get, prepare simple composite additive, to improve the stability in storage of straight distillation light diesel oil, secondary processing solar oil or its mixing oil.
Additive for stability of diesel oil provided by the invention is to be combined by tertiary amine (component I) and shielding phenol (component I I), and the weight ratio of tertiary amine and shielding phenol is 3~5: 1, and wherein the structural formula of tertiary amine is:
Figure C9310428900041
R in the formula 1, R 2Be C 1~C 10Alkyl, C preferably 7~C 10Alkyl; R 3Be C 6~C 18Alkyl, C preferably 7~C 10Alkyl; Shielding phenol is selected from 2,6 ditertiary butyl p cresol, 2,6-di-t-butyl mixed phenol.
Composite additive of the present invention can prepare by following method: tertiary amine and shielding phenol are added in the blending container by a certain percentage, are heated to 40~60 ℃ under the normal pressure, stir the yellow thick liquid product that promptly obtained homogeneous transparent in 1~2 hour.
Described 2.6-ditertbutylparacresol, commodity are called T501, and Jinzhou petroleum chemical plant is produced; 2.6-being Beijing Chemical Factory No. 3, produces the di-t-butyl mixed phenol.This type shielding phenol is oil product oxidation inhibitor commonly used, and it can suppress the rotten and generation colloid of oxidized.
Described tertiary amine is selected from N, N-dimethyl lauryl amine, N, N-dimethyl stearyl amine, N, N-dimethylcyclohexylamine, C 7~C 10Alkyl tertiary amine, C 8~C 10Alkyl tertiary amine.They are produced by Dalian Grease Chemical Plant.
Additive for stability of the present invention can be used for straight-run diesel oil, catalytic cracking diesel oil or through the catalytic cracking diesel oil of soda finishing or the mixing oil of straight-run diesel oil and catalytic cracking diesel oil, its add-on is 50~150mg/L diesel oil.
Major advantage of the present invention is: composite additive all has improvement to the stability in storage of straight distillation light diesel oil and secondary processing solar oil, not only make the formation speed of oil product sediment become slow, and the inhibition gelationus increases, still can satisfy service requirements through storing contained sediment and colloid for a long time, the long-time storage test of oil tank in the open shows further that also additive of the present invention has good effect to suppressing the generation of sediment and gelationus; To straight-run diesel oil or through the catalytic cracking diesel oil of soda finishing, add additive of the present invention, the stability better effects if, after adding agent as the catalytic cracking diesel oil of soda finishing, not only suppress sediment and gelationus and form, and the speed that color degenerates reduces normal temperature storage 50 days, the colour specification that still can satisfy first grade requires: store the engine performance test that adds agent diesel oil by oil tank and show that additive of the present invention has no adverse effects to performances such as diesel motor power, oil consumption, row's temperature, smoke evacuations; Components of additives of the present invention is easy to get, and preparation technology is simple, but also has advantages such as oil soluble is good, stable.
Further describe characteristics of the present invention with example below.
Example 1~6
Example 1~6 is additive product of the present invention and main character.
Component I and component I I are added in the blending container in proportion, and normal pressure heats 40~60 ℃ down, stirs 1~2 hour, and the thick liquid that obtains the yellowish brown of homogeneous transparent is product of the present invention.The results are shown in Table 1.
Table 1
Example The product code name Product is formed Reaction conditions Product property
Component I Component I I Component I: component I I Temperature ℃ Time h Outward appearance Nitrogen content % Base number mgKOH/g
1 2 3 4 5 6 A B C D E F N, N-dimethylcyclohexylamine N, N-dimethyl lauryl amine N, N-dimethyl stearyl amine C 7~C 10Alkyl tertiary amine C 7~C 10Alkyl tertiary amine C 8~C 20Alkyl tertiary amine T501 2,6-di-t-butyl mixed phenol T501 T501 2.6-di-t-butyl mixed phenol T501 3∶1 5∶1 5∶1 5∶1 5∶1 3∶1 50~ 60 50~ 60 50~ 60 40~ 50 40~ 50 40~ 50 2 1 1 1 1 2 The pale brown look liquid of the pale brown look liquid of the pale brown look liquid of yellow liquid yellow liquid yellow liquid 4.34 4.38 2.47 3.1 1.66 2.8 196.0 191.8 119.1 101.8 114.4 90.5
Example 7
This example is for improving catalytic cracking diesel oil storage at normal temperature gelationus effect.
Test oil is a catalytic cracking diesel oil.Colloid is pressed the GB509 method and is measured.The results are shown in Table 2.
Table 2
Title Additive add-on mg/L The storage at normal temperature colloid, mg/100ml
0d 10d 20d 40d 70d
Catalytic cracking diesel oil 0 18.0 41.4 46.0 79.9
Catalytic cracking diesel oil+additive D 120 18.0 20.2 31.0 38.6 44.0
Catalytic cracking diesel oil+additive F 120 18.0 19.6 24.2 36.0 42.8
Example 8
This example is to improve the effect that the diesel oil storage at normal temperature forms sediment.
Test oil is a catalytic cracking diesel oil.Storage requirement is that normal temperature lucifuge vial is stored.Employing SH/T0238-92 method mensuration catalytic cracking diesel oil is at the formed sediment of lay up period and accelerated storage sediment numerical value in 100 ℃ * 16 hours, and it the results are shown in Table 3.
Table 3
Title Additive add-on mg/L The normal temperature storage sediment, mg/100l Accelerate the storage sediment, mg/100ml
0d 15d 30d 50d 0d 15d 30d
Catalytic cracking diesel oil 0 0.01 0.21 0.66 3.60 0.14 0.39 2.80
Catalytic cracking diesel oil+A 150 0.02 0.11 0.13 0.87 0.31 0.41 1.23
Catalytic cracking diesel oil+B 120 0.01 0.10 0.24 1.15 0.30 0.54 1.63
Catalytic cracking diesel oil+C 120 0.04 0.14 0.36 1.34
Catalytic cracking diesel oil+D 120 0.05 0.05 0.19 1.04 0.04 0.14 0.26
Catalytic cracking diesel oil+E 120 0.03 0.10 0.10 1.81 0.41 0.79 2.14
Catalytic cracking diesel oil+F 150 0 0.09 0.44
Example 9
This example is an effect of improving catalytic cracking diesel oil and the catalytic cracking diesel oil storage stability behind soda finishing.Storage requirement is with example 8.The additive add-on is a 120mg/L diesel oil.The results are shown in Table 4.
Table 4
Title The storage at normal temperature colloid, mg/100ml Accelerate the storage sediment, mg/100ml
0d 15d 50d 0d 15d 30d 50d
Catalytic cracking diesel oil 20.6 25.4 76.4 0.14 0.39 2.80 5.81
Catalytic cracking diesel oil+D 12.4 17.8 54.0 0.04 0.14 0.26 2.23
The soda finishing catalytic cracking diesel oil 13.0 18.6 18.9 0.09 0.06 0.10 0.34
Soda finishing catalytic cracking diesel oil+D 8.0 8.6 16.4 0.10 0.10 0.14 0.10
Example 10
This example is that the trade mark of additive for stability of diesel oil of the present invention and abroad Du Pout company, Exxon company, the production of Ethyl company is respectively the storage stability simultaneous test of FOA, ECA, EDA additive for stability of diesel oil (seeing the products catalogue of above-mentioned company).Test oil is a catalytic cracking diesel oil.Storage requirement is with example 8.The results are shown in Table 5.Relative proportion numerical value is for the colloid that do not add agent diesel oil (blank oil) and obtain or accelerate and store sediment and be decided to be 100 in the table, adds agent diesel oil colloid or accelerates and store sediment with the colloid that does not add agent diesel oil or accelerate and store sediment and compare and obtain relative proportion numerical value.This numerical value is more little, and it is good more to improve the oil stability effect.
Table 5
The additive code name Add-on mg/L Colloid generates relative proportion % Sediment generates relative proportion, %
0 100 100
FOA-11 FOA-301 FOA-401 100 100 100 83.2 100 82.2 26.7 56.6 81.6
ECA8442 100 91.1 76.4
EDA-2 EDA-3 100 100 112 108.4 35.6 35.6
D F 100 100 60.0 76.7 13.2 23.2
Example 11
This example is the industrial performance test result.
Test oil is the catalytic cracking diesel oil through 3~5%NaOH soda finishing, adds additive for stability of the present invention, and it is stored in 10000M respectively 3In oil tank and the 200L oil drum, and with do not add agent soda finishing diesel oil and carry out the 200L oil drum and store simultaneous test.
Oil tank places open-air tank station, and the oil temperature is an envrionment temperature.The oil drum outdoor storage avoids daylight directly to shine.The results are shown in table 6, table 7.The data of table 6, table 7 are for from oil tank with store storage colloid that the oil sample that takes out in the oil drum measures after filtering and the sediment result who accelerates shelf test under 100 ℃ * 16h condition.
Table 6
Product Add-on, mg/l The storage at normal temperature colloid, mg/100l Remarks
0d 10d 20d 30d 50d 70d 90d
The soda finishing catalytic cracking diesel oil 0 44.2 52.6 60.0 74.6 87.4 115 The 200L bucket is stored
Soda finishing catalytic cracking diesel oil+D 120 25.2 31.8 38.6 39.0 53.6 52.4 74 The 200L bucket is stored
Soda finishing catalytic cracking diesel oil+D 120 25.8 29.6 36.2 50.2 54.2 73.6 10000 oil tanks are stored
Table 7
Product Add-on, mg/l Accelerate the storage sediment, mg/l Remarks
0d 10d 20d 30d 50d 70d 90d
The soda finishing catalytic cracking diesel oil 0 0.18 0.34 0.43 0.73 1.30 2.50 4.19 The 200L bucket is stored
Soda finishing catalytic cracking diesel oil+D 120 0.21 0.46 0.57 0.46 1.01 1.23 The 200L bucket is stored
Soda finishing catalytic cracking diesel oil+D 120 0.35 0.29 0.47 0.79 1.23 1.70 10000M 3Oil tank is stored
Found out that by table 6 blank catalytic cracking diesel oil is stored not enough 30d, existent gum just surpasses solar oil specification (being not more than 70mg/100ml) requirement, adds agent and can extend to 90d and jar store.Find out by table 7, add agent catalytic cracking diesel oil the sediment of accelerating stability restraining effect also clearly.

Claims (4)

1, a kind of additive for stability of diesel oil is characterized in that it is to be combined by tertiary amine (component I) and shielding phenol (component I I), and its weight ratio is that component I: component I I is 3~5: 1, and wherein the component I structural formula is:
Figure C9310428900021
R in the formula 1, R 2Be C 1~C 10Alkyl, R 3Be C 6~C 18Alkyl.
2,, it is characterized in that component I is selected from N, N-dimethyl lauryl amine, N, N-dimethyl stearyl amine, N, N-dimethylcyclohexylamine, C according to the described additive of claim 1 7~C 10Alkyl tertiary amine.
3,, it is characterized in that component I I is selected from 2,6 ditertiary butyl p cresol, 2,6-di-t-butyl mixed phenol according to the described additive of claim 1.
4,, it is characterized in that can be used for straight-run diesel oil, catalytic cracking diesel oil or through the catalytic cracking diesel oil of soda finishing or the mixing oil of straight-run diesel oil and catalytic cracking diesel oil, its consumption is 50~150mg/L diesel oil according to the described additive of claim 1.
CN93104289A 1993-04-23 1993-04-23 Additive for stability of diesel oil Expired - Fee Related CN1035883C (en)

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CN1035883C true CN1035883C (en) 1997-09-17

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010195973A (en) * 2009-02-26 2010-09-09 Hideaki Makita Fuel oil composition
CN101709232B (en) * 2009-11-11 2012-07-25 济南开发区星火科学技术研究院 Additive for oxidation stability of diesel oil
JP2011105872A (en) * 2009-11-18 2011-06-02 Hideaki Makita Fuel for internal combustion engine
CN102071076A (en) * 2009-11-24 2011-05-25 济南开发区星火科学技术研究院 Additive for prolonging induction period of gasoline and application method thereof
CN102703140B (en) * 2012-05-18 2014-08-20 上海保能环保节能材料科技有限公司 Fuel oil storage stabilizer with good compatibility and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137330A (en) * 1962-12-03 1964-06-16 Pioneers Proc Equipment Egg handling machinery
US4501595A (en) * 1984-05-25 1985-02-26 Texaco Inc. Middle distillate fuel oil of improved storage stability containing condensate of Mannich base and alkenyl succinic acid anhydride

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137330A (en) * 1962-12-03 1964-06-16 Pioneers Proc Equipment Egg handling machinery
US4501595A (en) * 1984-05-25 1985-02-26 Texaco Inc. Middle distillate fuel oil of improved storage stability containing condensate of Mannich base and alkenyl succinic acid anhydride

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