CN103289760A - Pour point depressant for diesel oil - Google Patents
Pour point depressant for diesel oil Download PDFInfo
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- CN103289760A CN103289760A CN2013101818982A CN201310181898A CN103289760A CN 103289760 A CN103289760 A CN 103289760A CN 2013101818982 A CN2013101818982 A CN 2013101818982A CN 201310181898 A CN201310181898 A CN 201310181898A CN 103289760 A CN103289760 A CN 103289760A
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- acrylic acid
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- tween
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Abstract
The invention discloses a pour point depressant for diesel oil, wherein polymethylacrylic acid higher ester is used as a host agent, and an arene compound, span, twain and a polar nitrogen-containing compound are used as an assistant. The substances are uniformly mixed and used for effectively reducing the cold filter plugging point of all diesel oils, and are especially better in perceptibility to diesel oils with high wax content and narrow fraction. In low temperature condition, the flowing property of diesel oils with high wax content and narrow fraction is better increased. The pour point depressant is simple to prepare, low in cost and remarkable in effect, has excellent market value, and can be used for solving the problem that the pour point depressant for diesel oil in the petrochemical industry in China is strong in pertinence, single in function and poor in broad spectrum.
Description
Technical field
The invention belongs to the petrochemical technology field, relate to a kind of diesel-dope, be specifically related to a kind of additive that reduces condensation point of diesel oil and cold filter clogging temperature.
Background technology
Diesel oil is a kind of multi-component complicated hydrocarbon mixture that contains, and can separate out the wax crystalline substance under low temperature condition, along with temperature descends, the wax crystalline substance increases, final form three-dimensional netted crystallization, when crystal is grown up to a certain degree will stopping up filter screen, thereby whole diesel motor can't be used.Therefore, improving the diesel oil at low-temperature flowability is to improve one of the subject matter that needs to be resolved hurrily of production of diesel oil.
The diesel pour inhibitor traditional in China generally is based on the ethylene-vinyl acetate development product, these products can only produce anti-condensation effect at one or more diesel oil, can not be common to all diesel oil, to content of wax height, the susceptibility of the diesel oil that cut is narrow is poor, so be difficult to terminal market supply again based on the pour point depressant of ethylene vinyl acetate exploitation.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of composite diesel pour point depressant is provided, be specifically related to a kind of pour point depressant that is common to all diesel oil, especially better to the susceptibility of the narrow diesel oil of content of wax height, cut, this diesel pour inhibitor not only can improve the cold filter clogging temperature effect fallen in diesel oil, and the pour point depressant cost is reduced, have favorable economic benefit, solved that existing China petrochemical industry diesel pour inhibitor exists with strong points, performance is single, the problem of broad spectrum difference.
A kind of diesel pour inhibitor, effective constituent is by weight:
The senior ester 30-45 of polymethyl acrylic acid part, aromatic hydroxy compound 30-50 part, sapn 10-20 part, tween 5-15 part, polarity nitrogenous compound 2-5 part.
The senior ester of described polymethyl acrylic acid is one or more in polymethyl acrylic acid ten diester, polymethyl acrylic acid 14 esters, polymethyl acrylic acid hexadecyl ester, the polymethyl acrylic acid octadecyl ester; Because the main component of diesel oil is alkane, cycloalkanes or the aromatic hydrocarbons that contains 10 to 22 carbon atoms, when the composition of alkyl acrylate is similar to the composition of N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN in the diesel oil, the pour point depression effect is best, so select the polymethacrylate of these four kinds of carbon atoms between 10 to 22 for use.
Described aromatic hydroxy compound is dimethylbenzene, because dimethylbenzene be adjacent, and the mixture of paraxylene, position dimethylbenzene between mostly being, and a position dimethylbenzene is very active, it can be adsorbed on the wax crystallization surface, influences wax crystallization and forms plate crystal, when more aromatic hydroxy compound exists, can link together two and above wax disk(-sc), thereby the wax crystalline substance is grown up.Eutectic effect in the diesel oil process of cooling helps the better of the brilliant particles dispersed of wax, is convenient to increase flowability of diesel oil.
Pour point depressant of the present invention, when the temperature reduction, when the wax crystalline substance has just formed, this pour point depressant will be separated out jointly or be adsorbed on the brilliant surface of wax with wax, make the brilliant particle granular of wax, and stop the wax intergranular to bond mutually to grow up, prevent from generating continuous crystallization net, make the brilliant particle of wax smoothly by filter screen, realized all significantly improving for the diesel oil that different refineries produce the purpose of low-temperature fluidity.
Both contained the polarity oxy radical in the polymethacrylate pour point depressant molecule that wherein adopts, contain the side chain non-polar group again, its pour-point depressing process is not only as alkylnaphthalene, pour point depressants such as ethylene-vinyl acetate base ester have adsorption, also have side chain alkyl and wax molecule cocrystallization at a certain temperature, and make brilliant connection of whole pour point depressant molecule and wax present " branch " shape, the wax crystalline substance is scattered in is difficult for growing up on " branch ", thereby play the eutectic effect that reduces the condensation point effect; Meanwhile stop the wax crystalline substance to be grown up because thereby the polar functionalities in the pour point depressant molecule can play, the condensation point of diesel oil and cold filter clogging temperature are reduced.
In order to increase the pour point depressant effect, the contriver has also added aromatic hydroxy compound, because the crystalline growth mode of wax is that the speed of being grown by X-axis and Z-direction is very fast in diesel oil, therefore forms big plate crystal easily, causes the flowability of diesel oil to weaken.And after adding above-mentioned aromatic hydroxy compound, it can be adsorbed on the wax crystallization surface, influences wax crystallization and forms plate crystal, and the eutectic effect in the diesel oil process of cooling helps the better of the brilliant particles dispersed of wax, is convenient to increase flowability of diesel oil.
Described sapn is one or more in span 20, sorbester p18, sorbester p17, the sorbester p37.Mainly be because the long alkyl chain of sapn can with the mutual effect of wax crystalline phase, make the two ends of wax crystalline substance have polarity, thereby crystal better disperses, can hinder the growth of wax crystalline substance again effectively.Simultaneously can also form aqueous surface, increase the lubricity between the crystal, thereby the probability that connects between the crystal is reduced, strengthen the effect of pour point depressant.
Described tween is one or more in polysorbas20, polysorbate40, tween 61, the tween 80.This material mainly act as nonionogenic tenside, mainly be because above-mentioned substance can play solublization as tensio-active agent in the diesel oil system, because tensio-active agent has the association colloid of formation, the micella kernel is non-polar group, skin is polar group, nonpolar all environment to polarity so just are provided, the suit environment that dissolves of the organism of various polarity can be provided.And because the surface tension of nonionogenic tenside is relatively low, so the micella that forms is also just more many, that forms micelle volume and will increase, and the space of energy solubilising is also just more many, and the amount of separating out of wax crystalline substance is just relatively more few, makes the filterableness of diesel oil just more good.
Described polarity nitrogenous compound is one or more in polyisobutene two inferior acid amides, trolamine, triethylene tetramine, tetraethylene pentamine, the polyethylene polyamine, it mainly is exactly because the polarity of above-mentioned substance is bigger, the effect that the wax crystalline substance is had dispersion, and the polarity in the molecular structure is partly pointed to oil phase, can prevent the further growth of wax crystalline substance.
In order further to improve result of use, the present inventor provides best technical scheme, described diesel pour inhibitor, and effective constituent is by weight:
40 parts of the senior esters of polymethyl acrylic acid, 40 parts of aromatic hydroxy compounds, 15 parts of sapns, 10 parts of tweens, 5 parts of polarity nitrogenous compounds;
The senior ester of described polymethyl acrylic acid is the polymethyl acrylic acid octadecyl ester, the nonpolar functional group number that polymethyl acrylic acid octadecyl ester side chain contains is many, make side chain alkyl group and the easier cocrystallization of wax molecule, more polarity oxy radical, stop the wax crystalline substance to be grown up, the easier condensation point of diesel oil and the cold filter clogging temperature of making reduces, and found through experiments in addition with the senior ester of other polymethyl acrylic acid and compares, and the polymethyl acrylic acid octadecyl ester is more similar to the composition of N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN in the diesel oil; Described aromatic hydroxy compound is dimethylbenzene, and described sapn is sorbester p37, and described tween is tween 80, and described polarity nitrogenous compound is triethylene tetramine.
Above-mentioned proportioning and the selection of material can reach best effect, after joining in the diesel oil, when the temperature reduction, when the wax crystalline substance has just formed, pour point depressant will be separated out jointly or be adsorbed on the brilliant surface of wax with wax, make the brilliant particle granular of wax, and mutual bonding the growing up of prevention wax intergranular, prevent from generating continuous crystallization net, make the brilliant particle of wax pass through filter screen smoothly, realized all significantly improving the diesel oil that different refineries produce the purpose of low-temperature fluidity, especially better to the susceptibility of the narrow diesel oil of content of wax height, cut.
The contriver discloses the method for preparing above-mentioned diesel pour inhibitor simultaneously, and concrete steps are:
Add earlier the senior ester series of polymethyl acrylic acid pour point depressant, add nonionogenic tenside sapn, tween, polarity nitrogenous compound successively then, add aromatic hydroxy compound at last to recipe quantity, fully mix composite product.
In sum, arylhydrocarbon in diesel oil compound provided by the present invention has adopted host and additive compound, the host of using is the senior ester series of polymethyl acrylic acid aromatic hydroxy compound, and the auxiliary agent that adopts is aromatic hydroxy compound, sapn, tween, the polarity nitrogenous compound, above-mentioned substance mixes cold filter clogging temperature and the condensation point that use can effectively reduce all diesel oil together, especially to content of wax height, the susceptibility of the diesel oil that cut is narrow is better, under cold condition, increased better content of wax height, the flowing property of the diesel oil that cut is narrow, and it is simple to have preparation, with low cost, effect is obvious, have splendid marketable value, solved with strong points that existing China petrochemical industry diesel pour inhibitor exists, performance is single, the problem of broad spectrum difference.
Embodiment
Further specify the present invention below in conjunction with embodiment, can make those skilled in the art more fully understand the present invention, but not limit the present invention in any way.
Embodiment 1:
The concrete set of dispense ratio of this pour point depressant is: nonionogenic tenside sapn-sorbester p17 of polymethyl acrylic acid ten diester of 45g, 30g aromatic hydroxy compound-dimethylbenzene, 12g, the another kind of non-ionic surfactant Tween-tween 61 of 5g, 3g polarity nitrogenous compound-trolamine.
Concrete preparation technology is: add polymethyl acrylic acid ten diester earlier, add nonionogenic tenside sapn, tween, polarity nitrogenous compound successively then, add aromatic hydroxy compound at last to recipe quantity, fully mix composite product.
Embodiment 2:
The concrete set of dispense ratio of this pour point depressant is: nonionogenic tenside sapn-span 20 of polymethyl acrylic acid 14 esters of 30g, 50g aromatic hydroxy compound-dimethylbenzene, 10g, the another kind of non-ionic surfactant Tween-polysorbas20 of 15g, 2g polarity nitrogenous compound-polyethylene polyamine.
Concrete preparation technology is: add polymethyl acrylic acid 14 esters earlier, add nonionogenic tenside sapn, tween, polarity nitrogenous compound successively then, add aromatic hydroxy compound at last to recipe quantity, fully mix composite product.
Embodiment 3:
The concrete set of dispense ratio of this pour point depressant is: nonionogenic tenside sapn-sorbester p18 of the polymethyl acrylic acid hexadecyl ester of 35g, 45g aromatic hydroxy compound-dimethylbenzene, 20g, the another kind of non-ionic surfactant Tween-polysorbate40 of 8g, 4g polarity nitrogenous compound-tetraethylene pentamine.
Concrete preparation technology is: add the polymethyl acrylic acid hexadecyl ester earlier, add nonionogenic tenside sapn, tween, polarity nitrogenous compound successively then, add aromatic hydroxy compound at last to recipe quantity, fully mix composite product.
Embodiment 4:
The concrete set of dispense ratio of this pour point depressant is: nonionogenic tenside sapn-sorbester p37 of the polymethyl acrylic acid octadecyl ester of 40g, 40g aromatic hydroxy compound-dimethylbenzene, 15g, the another kind of non-ionic surfactant Tween-tween 80 of 10g, 5g polarity nitrogenous compound-triethylene tetramine.
Concrete preparation technology is: add earlier the polymethyl acrylic acid octadecyl ester, then add successively nonionogenic tenside sapn, tween, polarity nitrogenous compound, add aromatic hydroxy compound to recipe quantity at last, fully mix composite product.
The test example
Diesel pour inhibitor A, B prepared among the embodiment 1-4, C, D are joined the content of wax respectively up in the diesel oil more than 60% (commercially available prod), and and commercially available diesel pour inhibitor simultaneous test, and adopt identical diesel oil and domestic fuel cold filter clogging temperature tester to measure, simultaneously measure its pour point depression effect with reference to SH/T0248-2006 diesel oil and domestic heating oil cold filter clogging temperature assay method, test result sees Table 1.
The effect comparison of table 1 diesel pour inhibitor of the present invention and commercially available pour point depressant
As can be seen from Table 1, commercially available diesel pour inhibitor is to the pour point depression DeGrain of the content of wax up to the diesel oil more than 60% (commercially available prod), and composite diesel pour point depressant of the present invention can significantly reduce the cold filter clogging temperature of diesel oil, especially the susceptibility of the narrow diesel oil of content of wax height, cut is better, the composite synergy that has played diesel oil of host and auxiliary agent, remedy existing pour point depressant and can not be common to all diesel oil, especially to content of wax height, the deficiency of the diesel oil susceptibility difference that cut is narrow.Wherein the cold filter clogging temperature of embodiment 4 is minimum, shows the pour point depression best results of composite diesel pour inhibitor.
Claims (6)
1. diesel pour inhibitor, it is characterized in that: effective constituent is by weight:
The senior ester 30-45 of polymethyl acrylic acid part, aromatic hydroxy compound 30-50 part, sapn 10-20 part, tween 5-15 part, polarity nitrogenous compound 2-5 part;
The senior ester of described polymethyl acrylic acid is one or more in polymethyl acrylic acid ten diester, polymethyl acrylic acid 14 esters, polymethyl acrylic acid hexadecyl ester, the polymethyl acrylic acid octadecyl ester;
Described aromatic hydroxy compound is dimethylbenzene.
2. diesel pour inhibitor according to claim 1, it is characterized in that: described sapn is one or more in span 20, sorbester p18, sorbester p17, the sorbester p37.
3. diesel pour inhibitor according to claim 1, it is characterized in that: described tween is one or more in polysorbas20, polysorbate40, tween 61, the tween 80.
4. diesel pour inhibitor according to claim 1, it is characterized in that: described polarity nitrogenous compound is one or more in polyisobutene two inferior acid amides, trolamine, triethylene tetramine, tetraethylene pentamine, the polyethylene polyamine.
5. diesel pour inhibitor according to claim 1, it is characterized in that: effective constituent is by weight:
40 parts of the senior esters of polymethyl acrylic acid, 40 parts of aromatic hydroxy compounds, 15 parts of sapns, 10 parts of tweens, 5 parts of polarity nitrogenous compounds;
The senior ester of described polymethyl acrylic acid is the polymethyl acrylic acid octadecyl ester, and described aromatic hydroxy compound is dimethylbenzene, and described sapn is sorbester p37, and described tween is tween 80, and described polarity nitrogenous compound is triethylene tetramine.
6. prepare the method for the described diesel pour inhibitor of claim 1, concrete steps are:
Add earlier the senior ester series of polymethyl acrylic acid pour point depressant, then add successively nonionogenic tenside sapn, tween, polarity nitrogenous compound, add aromatic hydroxy compound to recipe quantity at last, fully mix composite product.
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| CN201310181898.2A CN103289760B (en) | 2013-05-16 | 2013-05-16 | Pour point depressant for diesel oil |
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| CN201310181898.2A CN103289760B (en) | 2013-05-16 | 2013-05-16 | Pour point depressant for diesel oil |
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Cited By (20)
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| CN103484177A (en) * | 2013-10-12 | 2014-01-01 | 西安嘉宏石化科技有限公司 | Low-temperature fluidity improver composition of diesel oil and preparation method of low-temperature fluidity improver composition |
| CN103642469A (en) * | 2013-12-12 | 2014-03-19 | 中国石油集团渤海钻探工程有限公司 | Preparation method of low solidifying point lubricating agent for drilling fluid |
| CN104531270A (en) * | 2014-12-11 | 2015-04-22 | 青岛佰众化工技术有限公司 | Compound pour point depressant and preparation method thereof |
| CN106947557A (en) * | 2017-04-25 | 2017-07-14 | 上海应用技术大学 | A kind of polymethylacrylic acid high-carbon esters diesel oil pour point reducer composition and preparation method thereof |
| CN107619692A (en) * | 2017-09-25 | 2018-01-23 | 常州市协旺纺织品有限公司 | A kind of preparation method of diesel pour inhibitor |
| CN107964433A (en) * | 2017-12-12 | 2018-04-27 | 天津大远科技有限公司 | A kind of diesel pour inhibitor and preparation method thereof |
| CN109053951A (en) * | 2018-09-07 | 2018-12-21 | 上海应用技术大学 | A kind of diesel oil pour point reducer composition, preparation method and applications |
| CN109135846A (en) * | 2018-09-07 | 2019-01-04 | 上海应用技术大学 | A kind of broad spectrum type diesel oil pour point reducer composition, preparation method and applications |
| CN109135848A (en) * | 2018-09-07 | 2019-01-04 | 上海应用技术大学 | A kind of latent solvent for diesel pour inhibitor composition and preparation method thereof |
| CN109306281A (en) * | 2018-11-06 | 2019-02-05 | 烟台索山机械有限公司 | A kind of pour depressant for lubricating oil and preparation method thereof |
| CN110093193A (en) * | 2019-05-30 | 2019-08-06 | 上海应用技术大学 | A kind of Compositional type diesel pour inhibitor and the preparation method and application thereof |
| CN110437900A (en) * | 2019-07-19 | 2019-11-12 | 上海应用技术大学 | A kind of surfactant compound pour-point depressant and its preparation method and application |
| CN110540879A (en) * | 2019-08-13 | 2019-12-06 | 上海应用技术大学 | Diesel oil pour point depressant composition and preparation method and application thereof |
| CN110564459A (en) * | 2019-08-13 | 2019-12-13 | 上海应用技术大学 | Diesel oil pour point depressant containing nonionic surfactant and preparation and application thereof |
| CN110564465A (en) * | 2019-08-13 | 2019-12-13 | 上海应用技术大学 | Diesel oil pour point depressant and preparation method and application thereof |
| CN110591779A (en) * | 2019-07-19 | 2019-12-20 | 上海应用技术大学 | High-efficiency biodiesel pour point depressant composition and preparation method and application thereof |
| CN111635792A (en) * | 2020-05-27 | 2020-09-08 | 上海中太行之光能源有限公司 | Environment-friendly antifreeze agent for diesel oil and preparation method thereof |
| CN111635801A (en) * | 2020-05-11 | 2020-09-08 | 江苏龙蟠科技股份有限公司 | PMMA-containing composite pour point depressant and preparation method and application thereof |
| CN111676072A (en) * | 2020-05-20 | 2020-09-18 | 上海应用技术大学 | Biodiesel pour point depressant composition, and preparation and application thereof |
| CN111718768A (en) * | 2020-05-30 | 2020-09-29 | 上海应用技术大学 | Polar nitrogen-containing diesel pour point depressant composition and preparation and application thereof |
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| CN103484177A (en) * | 2013-10-12 | 2014-01-01 | 西安嘉宏石化科技有限公司 | Low-temperature fluidity improver composition of diesel oil and preparation method of low-temperature fluidity improver composition |
| CN103484177B (en) * | 2013-10-12 | 2015-06-10 | 西安嘉宏石化科技有限公司 | Low-temperature fluidity improver composition of diesel oil and preparation method of low-temperature fluidity improver composition |
| CN103642469A (en) * | 2013-12-12 | 2014-03-19 | 中国石油集团渤海钻探工程有限公司 | Preparation method of low solidifying point lubricating agent for drilling fluid |
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| CN110093193A (en) * | 2019-05-30 | 2019-08-06 | 上海应用技术大学 | A kind of Compositional type diesel pour inhibitor and the preparation method and application thereof |
| CN110093193B (en) * | 2019-05-30 | 2021-07-20 | 上海应用技术大学 | Compound diesel pour point depressant and preparation method and application thereof |
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| CN111676072A (en) * | 2020-05-20 | 2020-09-18 | 上海应用技术大学 | Biodiesel pour point depressant composition, and preparation and application thereof |
| CN111635792A (en) * | 2020-05-27 | 2020-09-08 | 上海中太行之光能源有限公司 | Environment-friendly antifreeze agent for diesel oil and preparation method thereof |
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