CN103641956A - Preparation method of diesel oil pour point depressant - Google Patents
Preparation method of diesel oil pour point depressant Download PDFInfo
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- CN103641956A CN103641956A CN201310725562.8A CN201310725562A CN103641956A CN 103641956 A CN103641956 A CN 103641956A CN 201310725562 A CN201310725562 A CN 201310725562A CN 103641956 A CN103641956 A CN 103641956A
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Abstract
The invention discloses a preparation method of a diesel oil pour point depressant. The preparation method comprises the following steps: (1) enabling polyisobutene to react with maleic anhydride to obtain polyolefin-based succinic anhydride; (2) enabling the polyolefin-based succinic anhydride to react with an initiator and high-level methacrylate to separate an intermediate product A; (3) adding the intermediate product A to react with a solvent and polyene polyamine completely to obtain the diesel oil pour point depressant. The diesel oil pour point depressant disclosed by the invention can be widely applied to the diesel oil of various trademarks, so that not only can cooling filter point effect on the diesel oil be improved, but also precursors of oil sludge, a film and carbon deposit can be dispersed in the oil to prevent the precursors from forming the oil sludge, the film and the carbon deposition, and therefore, service life of an internal combustion engine is prolonged.
Description
Technical field
The present invention relates to diesel-dope technical field, particularly relate to a kind of preparation method of diesel pour inhibitor.
Background technology
Diesel pour inhibitor, is to reduce the condensation point of crude oil and a kind of auxiliary agent of condensation point, in refining of petroleum industry and transportation, has important application.Diesel oil is a kind of multi-component complicated hydrocarbon mixture that contains, the carbon number of diesel oil institute hydrocarbonaceous is between 10-20, under low temperature condition, can separate out wax crystalline substance, along with temperature declines, wax crystalline substance increases, the three-dimensional netted crystallization of final formation, grows up and will stop up filter screen to a certain extent when crystal, thereby whole diesel motor cannot be used.Pour point depressant can reduce condensation point and the cold filter clogging temperature of crude oil greatly, the most economical method of most convenient is in pipeline, to add pour point depressant, alkyl wax in diesel oil is occurred with tiny crystallized form, hinder wax intergranular and form three-dimensional netted crystallization, thereby make diesel oil keep good low-temperature fluidity, facilitate accumulating and the use of diesel oil.And domestic and international wide model is applied low-molecular-weight ethene-acetate ethylene copolymer as diesel pour inhibitor at present.Although it can change diesel low-temperature liquidity, make diesel oil normal use under low temperature environment, can not be common to all diesel oil, high to the content of wax, the susceptibility of the diesel oil that cut is narrow is poor.
Summary of the invention
Object of the present invention is exactly that a kind of preparation method of diesel pour inhibitor is provided for the defect of above-mentioned existence.This diesel pour inhibitor can be widely used in various trade mark diesel oil, not only can improve cold filter clogging temperature effect fallen in diesel oil, also possess the precursor of greasy filth, paint film and carbon deposit is dispersed in oil simultaneously, stop it to form greasy filth, paint film and carbon deposit, extend the oil draining period, thereby extend the work-ing life of oil engine.
Preparation method's technical scheme of a kind of diesel pour inhibitor of the present invention is to comprise the following steps:
(1) under nitrogen protection, add polyisobutene and maleic anhydride, stir and be warming up to 140-200 ℃ simultaneously, reaction 6-8h, blows unreacted maleic anhydride off with nitrogen, obtains polyolefin-based Succinic anhydried;
(2) under nitrogen protection, add polyolefin-based Succinic anhydried, be warming up to 80-120 ℃, add initiator, stir, add higher alkyl methacrylate, reaction 6-8h, isolation of intermediate products A;
(3) add intermediate product A and solvent, under nitrogen protection, be warming up to 80-120 ℃, add polyamines polyene, react 5-8h, after reacting completely, obtain diesel pour inhibitor.
In step (1), the molecular weight of polyisobutene is 1000-6000, preferably 1000-3000.Polyisobutene and maleic anhydride mol ratio are 1:1-3.
Higher alkyl methacrylate molecular formula is in step (2), n=16-22 wherein, m=31-43.
In step (2), higher alkyl methacrylate and polyolefin-based Succinic anhydried mol ratio are 1-10:1.
Initiator described in step (2) is at least one in Benzoyl Peroxide, di-t-butyl peroxide, the tertiary butane of peroxidation; Initiator addition accounts for the 0.1%-5% of reactant weight.
In step (3), solvent quality is the mass percent 10-30% that accounts for A.
In step (3), A and polyamines polyene mol ratio are 1:1-3.
Polyamines polyene described in step (3) is at least one in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines.
Higher alkyl methacrylate described in step (3) is at least one in methacrylic dodecyl gallate, tetradecyl methylacrylate, methacrylic acid hexadecyl ester, stearyl methacrylate.The carbon number of diesel oil institute hydrocarbonaceous is between 10-20, and when the composition of higher alkyl methacrylate and the composition of N PARAFFIN & HEAVY NORMAL PARAFFIN in diesel oil are when similar, pour point depression effect is best, so select the higher alkyl methacrylate of these four kinds of carbon atoms between 10 to 22.
Solvent described in step (3) is at least one in benzene,toluene,xylene.Preferred dimethylbenzene, in dimethylbenzene preferably between position dimethylbenzene; Between position dimethylbenzene very active, it can be adsorbed on wax crystallization surface, affect wax crystallization formation plate crystal, when more aromatic hydroxy compound exists, two and above wax disk(-sc) can be linked together, thereby wax crystalline substance is grown up.Eutectic effect in diesel oil process of cooling, contributes to the better of the brilliant particle dispersion of wax, is convenient to increase flowability of diesel oil.Synthetic product of the present invention had both contained polarity oxy radical, contain again non-polar group, its pour-point depressing process is not only as alkylnaphthalene, the pour point depressants such as ethylene-vinyl acetate base ester have adsorption, also there is side chain alkyl and wax molecule cocrystallization at a certain temperature, and make whole pour point depressant molecule and interconnection of paraffin crystalline particles present " branch " shape, wax crystalline substance is scattered on " branch " and is difficult for growing up, thereby play the eutectic effect that reduces condensation point effect; Meanwhile because thereby the polar functionalities in pour point depressant molecule can play, stop wax crystalline substance to be grown up, the condensation point of diesel oil and cold filter clogging temperature are reduced.
Owing to introducing the amido that polarity is larger in compound, wax crystalline substance is there is to the effect of dispersion, and the sensing of the polar portion in molecular structure oil phase, can prevent the further growth of wax crystalline substance.
Beneficial effect of the present invention is: because the synthetic compound of the present invention has both contained polar group, had and contain nonpolar group, make diesel oil have good dispersion effect, the precursor of greasy filth, paint film and carbon deposit is dispersed in oil, stops it to form greasy filth, paint film and carbon deposit.
The present invention has following technique effect:
(1) adopt the senior fat of methacrylic acid, maleic anhydride, polyamines polyene is original, after reaction, without processing solvent, technique is simple;
(2) diesel pour inhibitor that the present invention produces can be applied to various trade mark diesel oil, is widely used;
(3) diesel pour inhibitor that the present invention produces not only can with wax molecule cocrystallization, and the polar functionalities in pour point depressant molecule can play and stop wax crystalline substance to be grown up, and the condensation point of diesel oil and cold filter clogging temperature are reduced.Pour point depressant also plays good dispersion effect simultaneously, and the precursor of greasy filth, paint film and carbon deposit is dispersed in oil, stops it to form greasy filth, paint film and carbon deposit, clean while guaranteeing diesel combustion, fuel saving.
Diesel pour inhibitor of the present invention is joined in commercially available diesel product as embodiment, according to the method for SH/T0249-92, survey cold filter point of diesel oil, investigate its pour point depression effect; And commercially available diesel pour inhibitor is added in above-mentioned commercially available diesel product as a comparison case, according to the method for SH/T0249-92, survey cold filter point of diesel oil, investigate its pour point depression effect; Result is as shown in table 1:
Table 1
embodiment:
In order to understand better the present invention, with specific examples, describe technical scheme of the present invention in detail below, but the present invention is not limited thereto.
embodiment 1
(1) polyolefin-based Succinic anhydried is synthetic: adding high-activity polyisobutene and maleic anhydride mol ratio is 1:1, stirs and is warming up to 140-200 ℃, and reaction 6h, blows unreacted maleic anhydride off with nitrogen, obtains polyolefin-based Succinic anhydried.
(2) under nitrogen protection, add polyolefin-based Succinic anhydried, be warming up to 80 ℃, be added in initiator Benzoyl Peroxide, initiator addition accounts for 1% of reactant weight, stir, add stearyl methacrylate, stearyl methacrylate and polyolefin-based Succinic anhydried mol ratio are 1:1, reaction 6h, isolation of intermediate products A;
(3) add the toluene of intermediate product A and A quality 10%, be warming up to 120 ℃ under nitrogen protection, add tetraethylene pentamine, A is that 1:1 reacts 5h with tetraethylene pentamine mol ratio, obtains product after reacting completely.
embodiment 2
(1) polyolefin-based Succinic anhydried is synthetic: adding high reactivity end thiazolinyl polyisobutene and maleic anhydride mol ratio is 1:2, stirs and is warming up to 140-200 ℃, and reaction 8h, blows unreacted maleic anhydride off with nitrogen, obtains polyolefin-based Succinic anhydried.
(2) under nitrogen protection, add polyolefin-based Succinic anhydried, be warming up to 100 ℃, be added in initiator Benzoyl Peroxide, initiator addition accounts for 0.1 of reactant weight, stir, add stearyl methacrylate, stearyl methacrylate and polyolefin-based Succinic anhydried mol ratio are 5:1, reaction 7h, isolation of intermediate products A;
(3) add the dimethylbenzene of intermediate product A and A quality 15%, be warming up to 80 ℃ under nitrogen protection, add tetraethylene pentamine, A is that 1:1.5 reacts 8h with tetraethylene pentamine mol ratio, obtains product after reacting completely.
embodiment 3
(1) polyolefin-based Succinic anhydried is synthetic: in three-necked bottle, adding high reactivity end thiazolinyl polyisobutene and maleic anhydride mol ratio is 1:3, stirring is warming up to 140-200 ℃, reaction 7h, blows unreacted maleic anhydride off with nitrogen, obtains polyolefin-based Succinic anhydried.
(2) under nitrogen protection, add polyolefin-based Succinic anhydried, be warming up to 120 ℃, be added in initiator Benzoyl Peroxide, initiator addition accounts for 5% of reactant weight, stir, add stearyl methacrylate, stearyl methacrylate and polyolefin-based Succinic anhydried mol ratio are 10:1, reaction 8h, isolation of intermediate products A;
(3) add the dimethylbenzene of intermediate product A and A quality 30%, be warming up to 100 ℃ under nitrogen protection, add tetraethylene pentamine, A is that 1:3 reacts 6h with tetraethylene pentamine mol ratio, obtains product after reacting completely.
The diesel pour inhibitor of embodiment of the present invention 1-3 is joined in commercially available diesel product, according to the method for SH/T0249-92, survey cold filter point of diesel oil, investigate its pour point depression effect; And commercially available diesel pour inhibitor is added in above-mentioned commercially available diesel product as a comparison case, according to the method for SH/T0249-92, survey cold filter point of diesel oil, investigate its pour point depression effect; Result is as shown in table 2:
Table 2
Claims (10)
1. a preparation method for diesel pour inhibitor, is characterized in that, comprises the following steps:
(1) under nitrogen protection, add polyisobutene and maleic anhydride, stir and be warming up to 140-200 ℃ simultaneously, reaction 6-8h, blows unreacted maleic anhydride off with nitrogen, obtains polyolefin-based Succinic anhydried;
(2) under nitrogen protection, add polyolefin-based Succinic anhydried, be warming up to 80-120 ℃, add initiator, stir, add higher alkyl methacrylate, reaction 6-8h, isolation of intermediate products A;
(3) add intermediate product A and solvent, under nitrogen protection, be warming up to 80-120 ℃, add polyamines polyene, react 5-8h, after reacting completely, obtain diesel pour inhibitor.
2. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, in step (1), the molecular weight of polyisobutene is 1000-6000; Polyisobutene and maleic anhydride mol ratio are 1:1-3.
3. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, higher alkyl methacrylate molecular formula is in step (2), n=16-22 wherein, m=31-43.
4. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, in step (2), higher alkyl methacrylate and polyolefin-based Succinic anhydried mol ratio are 1-10:1.
5. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, the initiator described in step (2) is at least one in Benzoyl Peroxide, di-t-butyl peroxide, the tertiary butane of peroxidation; Initiator addition accounts for the 0.1%-5% of reactant weight.
6. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, in step (3), solvent quality is the mass percent 10-30% that accounts for A.
7. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, in step (3), A and polyamines polyene mol ratio are 1:1-3.
8. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, the polyamines polyene described in step (3) is at least one in diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines.
9. the preparation method of a kind of diesel pour inhibitor according to claim 1, it is characterized in that, the higher alkyl methacrylate described in step (3) is at least one in methacrylic dodecyl gallate, tetradecyl methylacrylate, methacrylic acid hexadecyl ester, stearyl methacrylate.
10. the preparation method of a kind of diesel pour inhibitor according to claim 1, is characterized in that, the solvent described in step (3) is at least one in benzene,toluene,xylene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112480307A (en) * | 2020-11-30 | 2021-03-12 | 辽宁石油化工大学 | Anhydride type binary polymer pour point depressant, synthetic method thereof and lubricating oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063057A (en) * | 2006-04-25 | 2007-10-31 | 雅富顿公司 | Diesel fuel compositions |
| CN101619248A (en) * | 2009-05-14 | 2010-01-06 | 上海九元石油化工有限公司 | Method for preparing novel environmental-friendly high-efficiency diesel pour inhibitor |
| CN101691507A (en) * | 2009-10-15 | 2010-04-07 | 济南开发区星火科学技术研究院 | Diesel pour point depressant and preparation method thereof |
| CN101724476A (en) * | 2009-09-14 | 2010-06-09 | 陕西科技大学 | Diesel oil pour point depressant and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063057A (en) * | 2006-04-25 | 2007-10-31 | 雅富顿公司 | Diesel fuel compositions |
| CN101619248A (en) * | 2009-05-14 | 2010-01-06 | 上海九元石油化工有限公司 | Method for preparing novel environmental-friendly high-efficiency diesel pour inhibitor |
| CN101724476A (en) * | 2009-09-14 | 2010-06-09 | 陕西科技大学 | Diesel oil pour point depressant and preparation method thereof |
| CN101691507A (en) * | 2009-10-15 | 2010-04-07 | 济南开发区星火科学技术研究院 | Diesel pour point depressant and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480307A (en) * | 2020-11-30 | 2021-03-12 | 辽宁石油化工大学 | Anhydride type binary polymer pour point depressant, synthetic method thereof and lubricating oil |
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Effective date of registration: 20180428 Address after: 276600 West Huaihailu Road section of Junan County, Linyi, Shandong Patentee after: Linyi Shinengde Environmental Protection Fuel Chemical Co.,Ltd. Address before: 250000 building 11, North Qilihe Road, Licheng District, Ji'nan, Shandong, China, 11 Patentee before: Xinghuo Sci. & Tech. Research Inst., Jinan Dev. Zone |
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Effective date of registration: 20200714 Address after: Room 401, unit 2, building 11, No.2, Qilihe Road, Licheng District, Jinan City, Shandong Province 250100 Patentee after: SHANDONG XINGHUO INTELLECTUAL PROPERTY SERVICE Co.,Ltd. Address before: 276600 west section of Junan County, Linyi City, Shandong Province, Huaihailu Road Patentee before: LINYI SHINENGDE ENVIRONMENTAL PROTECTION FUEL CHEMICAL Co.,Ltd. |
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Effective date of registration: 20201228 Address after: Room 608, 6 / F, Zhongxing business enterprise development center, Pingshang Town, Lingang Economic Development Zone, Linyi City, Shandong Province Patentee after: Linyi Xinghuo Intellectual Property Service Co.,Ltd. Address before: Room 401, unit 2, building 11, No.2, Qilihe Road, Licheng District, Jinan City, Shandong Province 250100 Patentee before: SHANDONG XINGHUO INTELLECTUAL PROPERTY SERVICE Co.,Ltd. |
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