CN101205489B - Fuel oil additive composition, preparation and use thereof - Google Patents
Fuel oil additive composition, preparation and use thereof Download PDFInfo
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- CN101205489B CN101205489B CN2006101653119A CN200610165311A CN101205489B CN 101205489 B CN101205489 B CN 101205489B CN 2006101653119 A CN2006101653119 A CN 2006101653119A CN 200610165311 A CN200610165311 A CN 200610165311A CN 101205489 B CN101205489 B CN 101205489B
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Abstract
The invention relates to a fuel oil additive compound and a preparation method taking animal and vegetable grease as raw materials and an application thereof. In particular, the fuel oil additive compound of the invention consists of the following components based on the weight percent: the fatty acid monoalkyl ester of 50 to 80 percent, the monoglyceride of 5 to 30 percent, the diglyceride of 2 to 15 percent, the triglyceride of 0 to 7 percent, the fatty acid amide of 0 to 20 percent and the free glycerin of 0.01 to 1 percent.
Description
Technical field
The present invention relates to a kind of fuel oil additive composition, its preparation method and application thereof.Particularly, the present invention relates to a kind of is fuel oil additive composition, its preparation method and the application of feedstock production with the grease.
Background technology
Because the needs of environmental protection, the sulphur nitrogen equal size in the oil fuel will further reduce, and this just requires to carry out the more unifining of the degree of depth.In the deep hydrogenation process, some oilness materials that oil fuel contains are removed, so the oilness of oil fuel reduces.Though use this oil fuel environmental protection, can cause the wearing and tearing aggravation of oil pump, even cause oil pump failure.When for example just having brought into use low-sulfur diesel-oil abroad, this phenomenon happens occasionally.For solving the problem of Lubricity of Low-Sulfur Diesel Fuels difference, the external method of usefulness usually is to add oiliness additive.The diesel oil sulphur content that China uses now generally is no more than 2000ppm, and the oilness problem of diesel oil does not also show; But will use low-sulfur diesel-oil the coming years; Just sulphur content is no more than 500ppm; The lower diesel oil of sulphur content possibly used in some big cities such as Beijing, Shanghai, if do not add slip additive in these diesel oil, the oilness problem will inevitably occur.
In addition, along with petroleum resources shortage and poor qualityization day by day, eighties of last century is since the nineties, risen again through Fischer-Tropsch process synthetic oil technology and is used widely day by day by synthetic gas.The oilness of synthetic fuel oil is relatively poor, needs to add oiliness additive.
Oil fuel oiliness additive commonly used at present mainly is that some are nitrogenous, the compound of oxygen, like amine, ester etc.Wherein because ester compound is nonnitrogenous; Can not increase the nitrogen content of oil fuel; Obtaining to pay close attention to widely, is main ingredient like the additive of describing among the patent US 6511520 with monoglyceride and derivative of fatty acid, wherein contains the monoglyceride of 5-25%; Contain other lipid acid chain triacontanol ester or the alkanolamine of 35-75% etc., also have the triglyceride of 0.1-20% in addition.This additive joins sulphur content and is lower than in the diesel oil of 500ppm and can effectively improves its oilness.
The composition of the additive of record is fairly simple among the patent US 6511520, only provides a notion substantially, does not relate to concrete preparation method.
Consider from another angle; If the oil fuel oiliness additive can be synthetic with the mode of a kind of more environmental friendliness (environment-friendly); For example, the plant-animal product if its main raw material can have drawn from then more is expected to help to reach the effect of environmental protection.
Summary of the invention
The purpose of this invention is to provide a kind of fuel oil additive composition, its preparation method and application.
Therefore, the present invention provides a kind of fuel oil additive composition, is benchmark with the gross weight of compsn, and it is formed as follows:
Lipid acid mono alkyl ester: 50-80%
Monoglyceride: 5-30%
Triglyceride: 2-15%
Triglyceride level: 0-7%
Fatty acid amide: 0-20%
Free glycerol: 0.01-1%.
The present invention also provides a kind of preparation method of fuel oil additive composition, may further comprise the steps:
(A) a kind of monohydroxy-alcohol and at least a grease that is selected from animal-plant oil carry out transesterification reaction;
(B) from reaction product, remove monohydroxy-alcohol and other impurity;
(C) as required, replenish not enough component, the composition of adjustment product to following scope:
Gross weight with compsn is a benchmark, forms as follows:
Lipid acid mono alkyl ester: 50-80%
Monoglyceride: 5-30%
Triglyceride: 2-15%
Triglyceride level: 0-7%
Fatty acid amide: 0-20%
Free glycerol: 0.01-1%.
The present invention also provides the above-mentioned compsn oil lubrication property Application of Additives that acts as a fuel.
The present invention also provides animal-plant oil to be used to prepare the application of oil fuel oiliness additive compsn.
Oil fuel oiliness additive of the present invention can improve the oilness of oil fuel; Its preparation is a raw material with the animal-plant oil, only needs through simple reaction, and production process is environmentally friendly, and cost is low; And the monohydroxy-alcohol and the employed catalyzer reusable edible that produce in the reaction process of preparation.
Embodiment
The composition of fuel oil additive composition of the present invention is following, is benchmark with the gross weight of compsn:
Lipid acid mono alkyl ester: 50-80%
Monoglyceride: 5-30%
Triglyceride: 2-15%
Triglyceride level: 0-7%
Fatty acid amide: 0-20%
Free glycerol: 0.01-1%.
In compsn of the present invention, the content of monoglyceride is preferably 7.0-25%, more preferably 7-20%.
In compsn of the present invention, the content of fatty acid amide is preferably 0.1-10%, and more preferably 0.5-10% is preferably 0.5-7.0% especially.
In compsn of the present invention, the content sum of monoglyceride and fatty acid amide is preferably 10.0-25%, more preferably 12.0-22.0%.
For preparing compsn of the present invention, can each commercially available component product be mixed, can obtain compsn of the present invention.
In a preferred embodiment of the invention, compsn of the present invention prepares in the following manner:
(A) a kind of monohydroxy-alcohol and at least a grease that is selected from animal-plant oil carry out transesterification reaction;
(B) from reaction product, remove monohydroxy-alcohol and other impurity;
(C) as required, replenish not enough component, the composition of adjustment product to following scope:
Gross weight with compsn is a benchmark, forms as follows:
Lipid acid mono alkyl ester: 50-80%
Monoglyceride: 5-30%
Triglyceride: 2-15%
Triglyceride level: 0-7%
Fatty acid amide: 0-20%
Free glycerol: 0.01-1%.
In (A) of the inventive method step; The reaction of monohydroxy-alcohol and animal-plant oil is preferably carried out in the presence of catalyzer; Any catalyst for reaction of this type of " alcohol-ester " that is applicable to all can adopt, and is preferably common acid, alkali and amine, preferred especially boiling point and the approaching organic amine of used monohydroxy-alcohol; For example boiling point is lower than 200 ℃ aminated compounds; Aminated compounds can be the simplification compound, also can be two or more mixtures, extremely preferred diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Diisopropylamine, N; N-dimethyl n propylamine, allylamine, n-Butyl Amine 99, isobutylamine, sec.-butylamine, TERTIARY BUTYL AMINE, hexahydroaniline, aniline, methylphenylamine, N, accelerine, para-totuidine, pyrroles's (divinyl imines) etc.In step (A), catalyzer---for example the consumption of Organic Amines is the heavy 0.1-50% of grease, preferred 5-25%.
In (A) of the inventive method step; Monohydroxy-alcohol can adopt common monohydroxy-alcohol; For example boiling point is lower than 200 ℃ low-carbon alcohol; The monohydroxy-alcohol that preferably contains 1-10 carbon atom, special particular methanol, ethanol, propyl alcohol, Virahol or butanols, amylalcohol, hexanol, enanthol, octanol etc. and their isomer, utmost point particular methanol and ethanol.Said monohydroxy-alcohol can use separately, also can mix use.
In (A) of the inventive method step, the animal-plant oil that is adopted can be for directly being derived from waste material in vegeto-animal grease, finished animal-plant oil, depleted animal-plant oil and the animal-plant oil course of processing etc.; Preferred acid number is no more than the grease of 5mg KOH/g, and special preferred source is from the animal-plant oil of occurring in natures such as VT 18, rapeseed oil, Trisun Oil R 80, butter, lard existence and the grease after the modification thereof; Also can be through modes such as distillation, alkali neutralization, esterifications makes its acid number be reduced to the grease that is no more than 5mg KOH/g.
In (A) of the inventive method step, alcohol: the grease weight ratio is preferably 1: 20-20: 1, more preferably 1: 10-10: 1, further be preferably 1: 5-5: and 1, the utmost point is preferably 1: 3-3: 1.
In step (A), reaction pressure is normal pressure or low pressure, is advisable to be no more than 1MPa.
In step (A), temperature of reaction is any suitable temperature, is preferably near the boiling temperature of the monohydroxy-alcohol that is adopted.
In step (A), the reaction times is 1-20 hour, preferred 2-10 hour.
In step (A), preferably adopt mechanical stirring device, or add cosolvent, like THF etc.,, improve speed of response to increase pure grease mutual solubility.
In step (B), the method for removing monohydroxy-alcohol and other impurity (comprising the catalyzer of for example in (A) step, introducing) comprises filtration, extraction, distillation etc., and (for example organic amines) such as monohydroxy-alcohol that is reclaimed and catalyzer can reuse.
In step (C), as required, the not enough component in can supplemental prod, with composition to the following scope of adjustment product:
Gross weight with compsn is a benchmark, forms as follows:
Lipid acid mono alkyl ester: 50-80%
Monoglyceride: 5-30%
Triglyceride: 2-15%
Triglyceride level: 0-7%
Fatty acid amide: 0-20%
Free glycerol: 0.01-1%.
During not enough component in the supplemental prod, can adopt the commercially available prod, or existing synthetic product.
Replenish after the insufficient component, each components contents reaches said scope in the finished product, wherein preferably reaches following scope:
The content of monoglyceride is preferably 7.0-25%, more preferably 7-20%;
The content of fatty acid amide is preferably 0.1-10%, and more preferably 0.5-10% is preferably 0.5-7.0% especially;
The content sum of monoglyceride and fatty acid amide is preferably 10.0-25%, more preferably 12.0-22.0%.
Compsn of the present invention can be used for oil fuel, improves its oilness, is particularly suitable for the improvement of low-sulfur diesel-oil, ultra-low-sulphur diesel, combined diesel oil and blended diesel oilness thereof.For example, in sulphur content is lower than the diesel oil of 500ppm, add 10-5000ppm, this additive of preferred 50-500ppm can improve the oilness of diesel oil greatly, reaches the request for utilization of national regulation.
Therefore, the present invention also provides animal-plant oil to be used to prepare the application of oil fuel oiliness additive compsn.
Oil fuel oiliness additive of the present invention can improve the oilness of oil fuel.Its preparation can be adopted animal-plant oil is raw material, is simple and easy to, and helps to reduce the price of examples of such additives compsn; Its preparation process is simple simultaneously, and for environmentally friendly, running cost is also low.
Below adopt embodiment that the present invention is described further, but the invention is not restricted to these concrete embodiment.
In each embodiment, adopt the reciprocal trier method of international high frequency (HFRR) to make an experiment, concrete operation method is seen ISO/DIS 12156-1.3 and ASTM D 6079.Wear scar diameter to record compares, and wear scar diameter is big more, and oilness is poor more.The index of the city derv fuel oil oilness of national regulation is that wear scar diameter is no more than 460 μ m.The base oil that adopts in the test is not for adding the low-sulfur diesel-oil of any additives, and essential property is seen table 1.
The essential property of table 1 base oil
Embodiment 1
In a three-necked bottle, add the refining rapeseed oil (acid number is 1mg KOH/g) of 200g, be heated to 65 ℃ under the violent stirring, add the n-Butyl Amine 99-methanol solution for preparing in advance then, n-Butyl Amine 99 is 20g, is 10% of vegetables oil; Methyl alcohol is 108g, and pure grease weight ratio is approximately 1: 2.React after 10 hours, reaction soln 100 ℃ of following underpressure distillation, is obtained compsn.Stratographic analysis shows, this compsn fatty acids methyl esters 65.44%, monoglyceride 18.69%, triglyceride 9.53%, triglyceride level 4.86%, acid amides 0.82%, free glycerol 0.72%.This compsn that in base oil, adds 200ppm, the wear scar diameter of HFRR test drops to 346 μ m, has reduced by 39%, has improved the oilness of base oil, the request for utilization that is up to state standards.
Embodiment 2
In a 500ml reaction kettle that is connected with nitrogen, add 200g refined soybean oil (acid number is 1.1mg KOH/g), 108g methyl alcohol (pure grease weight ratio is approximately 1: 2) and 20g isobutylamine (for vegetables oil 10%) back seals; Under 100 ℃, 0.6MPa, violent stirring behind the reaction 6h; Underpressure distillation methyl alcohol and isobutylamine; Obtain said composition; Through stratographic analysis, its fatty acids methyl esters 78.11%, monoglyceride 7.49%, triglyceride 3.36%, triglyceride level 1.18%, acid amides 5.82%, free glycerol 0.56%.In base oil, add this compsn 150ppm, the HFRR wear scar diameter drops to 382 μ m, has reduced by 33%, has improved the oilness of base oil, the request for utilization that is up to state standards.
Embodiment 3
In a three-necked bottle, add the refining rapeseed oil (acid number is 0.9mg KOH/g) of 200g, be heated to 80 ℃ under the violent stirring, add pre-configured n-Butyl Amine 99-ethanolic soln then, n-Butyl Amine 99 is 30g, is 15% of vegetables oil; Ethanol is 150g, and pure grease weight ratio is 3: 4.React after 12 hours, reaction soln 100 ℃ of following underpressure distillation, is obtained additive.Stratographic analysis shows, this additive fatty acids ethyl ester 60.08%, monoglyceride 20.62%, triglyceride 9.73%, triglyceride level 5.53%, free glycerol 0.42%.This additive that in base oil, adds 150ppm, the wear scar diameter of HFRR test drops to 400 μ m, has reduced by 30%, has improved the oilness of base oil, the request for utilization that is up to state standards.
Embodiment 4
In a 500ml reaction kettle that is connected with nitrogen, add 200g refined soybean oil (acid number is 0.8mg KOH/g), 150g methyl alcohol (pure grease weight ratio is 3: 4) and 40g aniline (for vegetables oil 20%) back seals; Under 70 ℃, violent stirring behind the reaction 4h; Reaction soln 100 ℃ of following underpressure distillation, is obtained compsn.Stratographic analysis shows, this compsn fatty acids methyl esters 62.25%, monoglyceride 19.71%, triglyceride 8.73%, triglyceride level 6.48%, free glycerol 0.52%.This compsn that in base oil, adds 180ppm, the wear scar diameter of HFRR test drops to 410 μ m, has reduced by 28%, has improved the oilness of base oil, the request for utilization that is up to state standards.
Claims (10)
1. fuel oil additive composition is a benchmark with the gross weight of compsn, forms as follows:
Lipid acid mono alkyl ester: 50-80%
Monoglyceride: 5-30%
Triglyceride: 2-15%
Triglyceride level: 0-7%
Fatty acid amide: 0-20%
Free glycerol: 0.01-1%.
2. according to the compsn of claim 1, wherein the content of monoglyceride is 7.0-25%.
3. according to the compsn of claim 1, wherein the content of fatty acid amide is 0.1-10%.
4. according to the compsn of claim 1, wherein the content sum of monoglyceride and fatty acid amide is 10.0-25%.
5. a method for compositions for preparing claim 1 comprises
(A) a kind of monohydroxy-alcohol and at least a grease that is selected from animal-plant oil carry out transesterification reaction;
(B) from reaction product, remove monohydroxy-alcohol and the material except that lipid acid mono alkyl ester, monoglyceride, triglyceride, triglyceride level, fatty acid amide, free glycerol and monohydroxy-alcohol;
(C) as required, replenish not enough component, the composition of adjustment product to following scope:
Gross weight with compsn is a benchmark, forms as follows:
Lipid acid mono alkyl ester: 50-80%
Monoglyceride: 5-30%
Triglyceride: 2-15%
Triglyceride level: 0-7%
Fatty acid amide: 0-20%
Free glycerol: 0.01-1%.
6. according to the method for claim 5, wherein (A) step is carried out in the presence of the approaching organic amine of a kind of boiling point and used monohydroxy-alcohol.
7. according to the method for claim 5, wherein in (A) step, the animal-plant oil that is adopted is the grease that acid number is no more than 5mg KOH/g.
8. according to the method for claim 5, wherein in step (C), each components contents reaches following scope in the adjustment the finished product:
The content of monoglyceride is preferably 7.0-25%;
The content of fatty acid amide is preferably 0.1-10%;
The content sum of monoglyceride and fatty acid amide is preferably 10.0-25%.
9. the compsn of claim 1 is used to improve the application of oil fuel oilness.
10. animal-plant oil is used to prepare the application of the oil fuel oiliness additive compsn of claim 1.
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| CN2006101653119A CN101205489B (en) | 2006-12-18 | 2006-12-18 | Fuel oil additive composition, preparation and use thereof |
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| CN2006101653119A CN101205489B (en) | 2006-12-18 | 2006-12-18 | Fuel oil additive composition, preparation and use thereof |
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| CN101205489B true CN101205489B (en) | 2012-01-25 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787318B (en) * | 2010-03-29 | 2013-01-09 | 辽宁石油化工大学 | Improver for lubricating performance of low-sulfur diesel oil and preparation process thereof |
| WO2012040175A1 (en) * | 2010-09-24 | 2012-03-29 | Dow Global Technologies Llc | Estolide derivatives prepared from triglycerides |
| CN102453562B (en) * | 2010-10-27 | 2014-04-30 | 中国石油化工股份有限公司 | Organic amide low-sulfur diesel oil lubrication additive and application thereof |
| CN103060030B (en) * | 2011-10-21 | 2015-04-29 | 中国石油化工股份有限公司 | Diesel additive composition containing alkyl ethylene glycol acetamide and application thereof |
| EP2871195A1 (en) * | 2013-11-07 | 2015-05-13 | ALLNEX AUSTRIA GmbH | Cationic Alkyd Resins |
| CN105695005A (en) * | 2016-04-12 | 2016-06-22 | 绵阳正合科技有限公司 | Gasoline additive and using method thereof |
| CN108070413A (en) * | 2017-08-25 | 2018-05-25 | 深圳合生能源科技有限公司 | A kind of polarization fuel oil additive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0543356B1 (en) * | 1991-11-22 | 1997-02-12 | Röhm Gmbh | Process for making compositions with improved low temperature behaviour |
| US20020017629A1 (en) * | 2000-08-02 | 2002-02-14 | Benjamin Mosier | Transesterification composition of fatty acid esters, and uses thereof |
| EP1230328A1 (en) * | 1999-11-17 | 2002-08-14 | Basf Aktiengesellschaft | Lubricity improver and a fuel and lubricant compositions containing said agent |
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2006
- 2006-12-18 CN CN2006101653119A patent/CN101205489B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0543356B1 (en) * | 1991-11-22 | 1997-02-12 | Röhm Gmbh | Process for making compositions with improved low temperature behaviour |
| EP1230328A1 (en) * | 1999-11-17 | 2002-08-14 | Basf Aktiengesellschaft | Lubricity improver and a fuel and lubricant compositions containing said agent |
| US20020017629A1 (en) * | 2000-08-02 | 2002-02-14 | Benjamin Mosier | Transesterification composition of fatty acid esters, and uses thereof |
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