CN1064305A - Lubricating oil, oil fuel and pour point depressant for crude oil - Google Patents
Lubricating oil, oil fuel and pour point depressant for crude oil Download PDFInfo
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- CN1064305A CN1064305A CN 92102530 CN92102530A CN1064305A CN 1064305 A CN1064305 A CN 1064305A CN 92102530 CN92102530 CN 92102530 CN 92102530 A CN92102530 A CN 92102530A CN 1064305 A CN1064305 A CN 1064305A
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- Prior art keywords
- pour point
- point depressant
- oil
- pour
- crude oil
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
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- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The present invention provides a kind of highly effective pour depressant for crude oil with high solidifying point and oil product.(carbon number is C to this pour point depressant through primary alconol with the multipolymer that mixes alpha-olefin by maleic anhydride
8～C
40, recommend to use C
18) mixed ester compound that obtains of esterification, add again and doubly measure aromatic solvent and make pour point depressant.Reduce to 15～13 ℃ for 23 ℃ in the time of can making Daqing crude oil condensation point (35 ℃ of GB510-83 condensation points) by pure thermal treatment in conjunction with 0.5～1.0% pour point depressant of 70 ℃ of thermal treatments addings, pure pour point depression degree is 8～10 ℃.Add 1.0% pour point depressant at 50 ℃ and can make 20# heavy gas oil condensation point, be reduced to 3 ℃ by 16 ℃, this pour point depressant also is applicable to other crude oil and oil product.
Description
The invention belongs to the polymer petrochemical industry, relate in particular to a kind of pour point depressant of preparation and reduce crude oil with high solidifying point, lubricating oil, oil product solidifying point solves its low-temperature fluidity problem.International Patent classificating number of the present invention is C10M.
Well-known homemade pour point depressant has the T801-alkylnaphthalene, the T803-poly-alpha olefins, T804-ethylene-vinyl acetate copolymer, and to polyacrylic acid normal chain alkyl ester and EVA(import pour point depressant) and the recombiner formed of tensio-active agent carried out the research of pour-point depressing process.Davis in 1931 obtain condenses pour point depressant (the being T801) patent of clorafin and naphthalene first, American-European countries and Japan have delivered many patent and papers about pour point depressant, these pour point depressants can be divided into following three classes substantially: (1) vinyl acetate polymer type, as US4362533, EP74208, the pour point depressant of R067487 report is 10 ℃ to the pour point depression degree of diesel oil spends to more than 10, and R067487 is 20 ℃ to the pour point depression of crude oil degree; (2) alkyl acrylate polymer-type such as US4419106, US4547202 is 25 ℃ to Norway＞650 heavy fuel oil (HFO) pour point depression degree; (3) maleic acid ester or fumarate class in polymer type, as EP156577, JP59138695, USSR1047951 to crude oil and diesel oil pour point depression degree about 20 ℃.Existing in sum pour point depressant level does not satisfy the demand of petroleum industry, so be necessary to develop suitable crude oil with high solidifying point, the pour point depressant that the pour point depression of diesel oil characteristics is effective, thereby improve the low-temperature fluidity of oil product, for example homemade T801, T803 is used for reducing the lubricating oil condensation point, and crude oil is not had pour-point depressing process, and is very little to the diesel oil pour-point depressing process; T804 is used for reducing condensation point of diesel oil, especially better to catalytic cracking diesel oil pour point depression effect, its pour point depression degree has only 6-7 ℃, and the existing applied pipeline transportation method of heating in crude oil piecemeal, its fuels and energy consumption is all very big, reduce the scheme of production diesel oil such as final boiling point, the one, restriction production of diesel oil, the 2nd, waste petroleum resources.If use the present invention can save heating fuel (as crude oil) concerning crude pipeline transportation, few electricity consumption saves some heating pumping plant and managerial personnel, and as using pour point depressant of the present invention, one can enlarge production of diesel oil to diesel oil; Two can improve diesel quality, its economic benefit and social benefit are apparent, the objective of the invention is synthetic a kind of pour point depressant and solve crude oil with high solidifying point, the diesel oil at low-temperature flowability problem, for reach crude oil normal temperature pipe-line transportation and solve the part production of diesel oil, quality problems lay the first stone.
The present invention prepares the method for pour point depressant and pour point depressant, and the method for synthetic pour point depressant was divided into for three steps:
The first step maleic anhydride with mix alpha-olefin copolymer
Maleic anhydride is under initiator (dicumyl peroxide) effect with the copolymerization that mixes alpha-olefin
The esterification of the second step intermediate product and primary alconol
Esterification is under catalyzer (tosic acid) effect, the esterification by ring opening reaction of the anhydride group on primary alconol and the copolymer chain, and its reaction equation is:
Through infrared, nuclear-magnetism (H spectrum), the mensuration of ultimate analysis and molecular-weight average etc., the structure of extrapolating pour point depressant is:
Wherein R is that average carbon atom number is 16 straight chained alkyl
R is that carbonatoms is from C
6-C
10
R ': be C
6-C
40Straight chained alkyl (promptly be equivalent to alcohol carbon number) optimum value be C
10
N: be mean polymerisation degree, when the average carbon atom number of R is 16, R ' carbonatoms is 18 o'clock, n=11, and this pour point depressant of M=9857 molecular weight distribution does not wait to tens0000 from hundreds of.This moment, structure was:
The synthetic of pour point depressant also can (carbon number be C on the ester group by maleic acid ester
6-C
40) (olefin carbon number is C with mixing alpha-olefin
6-C
40) copolymerization and getting
The mixed pour point depressant that gets of the 3rd step mixed ester compound and aromatic solvent, mixed ester compound and aromatic solvent were by 1: 1 mixed, and aromatic solvent comprises toluene, and various dimethylbenzene and xylol also can be made for example C of solvent with ester fat hydrocarbon
10Alkane.
Effect of the present invention depends on the pour point depression effect of pour point depressant, and pour point depression effect and formation testing character, the acid anhydride alkene ratio when synthetic, the influence factors such as cooling rate of the dosage of pour point depressant, use temperature and formation testing are relevant, with Daqing crude oil and Anshan 20# heavy gas oil is example, investigate pour point depression effect and above-mentioned all influence factors of pour point depressant, thereby draw the condition of using pour point depressant:
1, influences the factor of pour point depressant pour point depression effect
(1) formation testing character
The formation testing character that influences zero pour mainly is meant colloid, bituminous matter and the wax in the formation testing.The composition of wax and content are the fundamental factor of decision zero pour, wax content height, zero pour height.Colloid, bituminous matter are natural pour point depressants, and as heating or fast cooling repeatedly, colloid, bituminous matter have little time to be adsorbed on the wax crystalline substance, and the wax crystalline substance is grown up rapidly and is linked to be netted and solidifies, just natural pour point depressant effect can not be brought into play.For example the Daqing crude oil zero pour is 35 ℃, and being preheated to 70 ℃, to record zero pour be 30 ℃, but as be cooled to 38 ℃ by 70 ℃ of preheating temperatures naturally together with hot water bath, recording zero pour is 23 ℃.Natural pour point depressant has been brought into play effect under latter event.Anshan 20# heavy gas oil is not owing to contain colloid, and the bituminous matter speed of no matter lowering the temperature records zero pour and is 16 ℃, and is above-mentioned all by GB510-83 method survey zero pour.
Acid anhydride alkene ratio when (2) synthesizing pour point depressant
By maleic anhydride with mix the alpha-olefin charge weight than different a series of pour point depressants, with 1.0%(wt) to add that dosage investigates the Daqing crude oil zero pour be that 35 ℃ and Anshan 20# heavy gas oil condensation point are 16 ℃ pour point depression effect.The results are shown in Table 1.As shown in Table 1 at acid anhydride alkene than 1: 6.29, the carbon number of the used alcohol of esterification is C
18The time synthetic pour point depressant, be Daqing crude oil and Anshan 20# heavy gas oil all to be had best pour point depression effect at 1.0% o'clock adding dosage.
Table 1 is with the pour point depression effect # of different acid anhydride alkene than synthetic pour point depressant
It is benchmark with the solid phase prod that # adds dosage, by weight.Zero pour is pressed GB510-83 and is measured, and is the mean value of three mensuration.The Daqing crude oil sample is preheated to 70 ℃ earlier, measures zero pour be cooled to 38 ℃ naturally in water-bath after.
Table 2 pour point depressant dosage and pour point depression effect relation #
# makes a bet referring to table 1.
Table 3 use temperature (preheating temperature) is to 1.0% pour point depressant
The influence of pour point depression effect
# makes a bet referring to table 1, and pre-temperature is a variable.
(3) influence of pour point depressant add-on
With acid anhydride alkene ratio is 1: the pour point depressant 6.29(1-stearyl alcohol) has carried out adding the investigation of dosage to the pour point depression effect.The results are shown in Table 2.Testing used adding in the dosage range, the zero pour of Daqing crude oil and Anshan 20# heavy gas oil all descends with the increase that adds dosage.To Daqing crude oil, the suitable dosage that adds is 0.5% to 1.0%, 8-10 ℃ of at this moment pure pour point depression Du Keda, and for 20# heavy gas oil, the suitable dosage that adds is 1.0%, pure pour point depression degree is 13 ℃.
(4) use temperature of pour point depressant
With acid anhydride alkene ratio is 1: the pour point depressant 6.29(1-stearyl alcohol), add dosage 1.0%, and investigate different use temperatures (being thermal treatment temp) and, the results are shown in Table 3 the influence of pour point depression effect.Pour point depressant is used for the Daqing crude oil pour point depression when handling, use temperature with 70-80 ℃ for well, can make depression of the freezing point 22 to 23 ℃ at this moment.In 50-90 ℃ of scope, use temperature does not have influence to the pour point depression effect for Anshan 20# heavy gas oil, therefore optional 50 ℃.
(5) influence of pour point depression speed
Cooling rate influences the pour point depression effect, and different formation testings has the different wax peak warm areas of analysing, and controls oily temperature lowering speed in this warm area, and pour point depressant is played one's part to the full.1.0% pour point depressant is added in 70 ℃ of heat treated Daqing crude oils, under more slowly cooling condition (70 → 38 ℃ average cooling rate be 8.9 ℃/h) pour point depressant can play one's part to the full, former oil freezing point minimum (13 ℃).Cooling rate is little to the pour point depression influential effect of Anshan 20# heavy gas oil.
Pour point depressant is to different formation testing pour point depression effect differences in sum, acid anhydride alkene ratio is that 1: 6.29 pour point depressant is best to the pour point depression effect of Daqing crude oil and Anshan 20# heavy gas oil, in conjunction with 70 ℃ of thermal treatments, add 0.5%～1.0% pour point depressant, more slowly the zero pour of Daqing crude oil can be reduced to 15 ℃ to 13 ℃ by 35 ℃ under cooling (70 ℃ → 38 ℃) condition, can be like this that Daqing crude oil normal temperature pipe is defeated to lay the first stone, the pour point depression effect descended when cooling rate raise.Add 1.0% pour point depressant at 50 ℃, can make the zero pour of Anshan 20# heavy gas oil reduce to 3 ℃ by 16 ℃.This pour point depressant also is applicable to other crude oil and oil product, is particularly useful for Daqing crude oil, 10 ℃ of its pour point depression Du Keda.
Embodiment
Agitator is being equipped with, logical nitrogen kapillary, add the mixing alpha-olefin after 31.0g makes with extra care in the 100ml three neck port grinding bottles of feed hopper and condensation reflux unit, 4.9g maleic anhydride, 0.4g dicumyl peroxide and 20ml toluene, logical nitrogen removes air in the white vase, start agitator, be heated to 130 ℃, isothermal reaction 4 hours, be chilled to and add 27.0g1-stearyl alcohol (or the primary alconol of other carbon number, or the mixing primary alconol of several carbon numbers), 0.8g tosic acid and 20ml dimethylbenzene after the room temperature, be warming up to 138 ℃, isothermal reaction 10 hours will constantly steam the water of generation in the reaction process, reactant is chilled to 70 ℃ to 80 ℃, wash and obtain mixed ester compound twice, adding is doubly measured aromatic solvent (toluene or dimethylbenzene) and is made pour point depressant again.
Claims (2)
1, a kind of preparation method who is used for the pour point depressant of crude oil with high solidifying point and oil product is characterized in that by the Malaysia
Mix alpha-olefin (CH
2=CH-R) under the effect of initiator (dicumyl peroxide), be t in temperature
1Free radical addition reaction in the time of=120～135 ℃ obtains the intermediate product multipolymer
, anhydride group on this copolymer chain and primary alconol (HOR ') are under catalyzer (tosic acid) effect, in temperature t
2The esterification by ring opening reaction takes place in the time of=130～140 ℃ obtain mixed ester compound
, mixed ester compound and aromatic solvent (toluene or dimethylbenzene) prepare pour point depressant by 1: 1 mixed, and wherein R is C
6～C
10Straight chained alkyl, average carbon atom number is 16, R ' is C
6～C
40Straight chained alkyl (be equivalent to alcohol carbon number), recommendation is C
16, n is a mean polymerisation degree.
2, a kind of pour point depressant that is used for crude oil with high solidifying point and oil product, it is characterized by pour point depressant is mixture, wherein contain 50%(wt) toluene or dimethylbenzene and 50%(wt) mixed ester compound, and mixed ester compound by maleic anhydride with mix alpha-olefin copolymer and obtain through the primary alconol esterification again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92102530 CN1026123C (en) | 1992-04-15 | 1992-04-15 | Coagulation reducing agent for lubricating oil, fuel oil and crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92102530 CN1026123C (en) | 1992-04-15 | 1992-04-15 | Coagulation reducing agent for lubricating oil, fuel oil and crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1064305A true CN1064305A (en) | 1992-09-09 |
| CN1026123C CN1026123C (en) | 1994-10-05 |
Family
ID=4939707
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92102530 Expired - Fee Related CN1026123C (en) | 1992-04-15 | 1992-04-15 | Coagulation reducing agent for lubricating oil, fuel oil and crude oil |
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| CN (1) | CN1026123C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870750A (en) * | 2010-06-02 | 2010-10-27 | 华东理工大学 | Comb copolymer, preparation method and application thereof |
| CN101899162A (en) * | 2010-07-16 | 2010-12-01 | 华东理工大学 | Comb-shaped polymer and preparation method and application thereof |
| CN103627450A (en) * | 2013-12-02 | 2014-03-12 | 济南开发区星火科学技术研究院 | Viscosity reducer for fuel oil and preparation method for viscosity reducer |
| CN107849180A (en) * | 2015-07-23 | 2018-03-27 | 萨索尔化学品性能有限公司 | Polymeric additive is used for the purposes of the fluid containing alkane |
| CN109321322A (en) * | 2018-10-16 | 2019-02-12 | 无锡棋成实业有限公司 | A kind of preparation of poly alpha olefin/esters synthesis lubricating base oil |
| CN110387002A (en) * | 2018-04-23 | 2019-10-29 | 广州精至百特利化工科技有限公司 | A kind of preparation of industrial oleic acid pour-point depressant and its application method |
| CN110964495A (en) * | 2019-11-01 | 2020-04-07 | 山东德仕石油工程集团股份有限公司 | Pour point depressant for crude oil and preparation method thereof |
| US11193053B2 (en) | 2017-04-13 | 2021-12-07 | Bl Technologies, Inc. | Wax inhibitors for oil compositions and methods of using wax inhibitors to reduce wax deposition from oil |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277144A (en) * | 2008-07-31 | 2015-01-14 | 卢布里佐尔公司 | Novel copolymers and lubricating compositions thereof |
-
1992
- 1992-04-15 CN CN 92102530 patent/CN1026123C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870750A (en) * | 2010-06-02 | 2010-10-27 | 华东理工大学 | Comb copolymer, preparation method and application thereof |
| CN101899162A (en) * | 2010-07-16 | 2010-12-01 | 华东理工大学 | Comb-shaped polymer and preparation method and application thereof |
| CN101899162B (en) * | 2010-07-16 | 2012-10-17 | 华东理工大学 | Comb-shaped polymer and preparation method and application thereof |
| CN103627450A (en) * | 2013-12-02 | 2014-03-12 | 济南开发区星火科学技术研究院 | Viscosity reducer for fuel oil and preparation method for viscosity reducer |
| CN107849180A (en) * | 2015-07-23 | 2018-03-27 | 萨索尔化学品性能有限公司 | Polymeric additive is used for the purposes of the fluid containing alkane |
| US11193053B2 (en) | 2017-04-13 | 2021-12-07 | Bl Technologies, Inc. | Wax inhibitors for oil compositions and methods of using wax inhibitors to reduce wax deposition from oil |
| US11261369B2 (en) | 2017-04-13 | 2022-03-01 | Bl Technologies, Inc. | Maleic anhydride copolymer with broadly dispersed ester side chain as wax inhibitor and wax crystallization enhancer |
| CN110387002A (en) * | 2018-04-23 | 2019-10-29 | 广州精至百特利化工科技有限公司 | A kind of preparation of industrial oleic acid pour-point depressant and its application method |
| CN109321322A (en) * | 2018-10-16 | 2019-02-12 | 无锡棋成实业有限公司 | A kind of preparation of poly alpha olefin/esters synthesis lubricating base oil |
| CN110964495A (en) * | 2019-11-01 | 2020-04-07 | 山东德仕石油工程集团股份有限公司 | Pour point depressant for crude oil and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1026123C (en) | 1994-10-05 |
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