CN104694181A - Novel diesel oil pour-point depressant - Google Patents
Novel diesel oil pour-point depressant Download PDFInfo
- Publication number
- CN104694181A CN104694181A CN201310651582.5A CN201310651582A CN104694181A CN 104694181 A CN104694181 A CN 104694181A CN 201310651582 A CN201310651582 A CN 201310651582A CN 104694181 A CN104694181 A CN 104694181A
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- alpha
- sma
- hexadecyl
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Lubricants (AREA)
Abstract
The invention relates to a novel diesel oil pour-point depressant, which is prepared by complex formulation of 50-60% of polyethylene vinyl acetate (T1804), 20-30% of hexadecyl methylacrylate maleic anhydride-alpha-alkene (SMA-MA alpha)copolymer, and 15-20% of toluene. The hexadecyl methylacrylate maleic anhydride-alpha-alkene takes hexadecyl methylacrylate, maleic anhydride and alpha-alkene as raw materials, under effect of a catalyst benzoyl peroxide, toluene is taken as a solvent, and solution polymerization is carried out to obtain a copolymer. The prepared novel diesel oil pour-point depressant can be used for diesel oil refined by cycloalkyl and paraffin-based crude oil, hexadecyl methylacrylate maleic anhydride-alpha-alkene and polyethylene vinyl acetate have good synergistic effect, so that cold filter plugging point of the diesel oil can be effectively reduced.
Description
Technical field
The invention belongs to oil dope field, be a kind of novel diesel pour inhibitor, effectively can reduce the cold filter clogging temperature of diesel oil.
Background technology
Synthetic pour point depressant is the earliest that Davis's oxidized petroleum waxs in 1931 and naphthalene obtain trade(brand)name paraflow pour point depressant through the reaction of Rui Dekelai Ford.Nineteen thirty-seven has delivered the patent of polymethacrylate.Within 1948, delivered alkyl styrenes, after this various new diesel pour inhibitor is developed rapidly, or has done improvement to the pour point depressant that oneself has.There is olefin polymer the fifties, occurred alkylphenol polymkeric substance the sixties, ethene and vinyl acetate ester copolymer.
The diesel pour inhibitor applied in the world now mainly contains following a few class:
A) vinyl acetate vinyl acetate copolymer.Vinyl acetate vinyl acetate copolymer uses the widest diesel pour inhibitor at present.As the paradyne20 of Exxon Corporation, paradyne25, ECA5920, the T1804 of China etc. all belong to this type of.
B) allyl butyrate diamide hydrochlorate.This is a kind of diesel pour inhibitor that effectively can improve low temperature flow strainability, within 1970, manufactures experimently production by Xue Fulong company.
C) vinyl acetate fumarate copolymer.This polymkeric substance has market application comparatively widely, as vinyl acetate-C12-C18 dialkyl fumarate multipolymer, vinyl acetate containing 40%-60% (molar fraction), average molecular mass is 1000kg/kmol-30000kg/kmol, addition is 0.03% (massfraction), and the CFPP of diesel oil can be made to decline about 8 DEG C.Paradyne80, para-dyne85 of Exxon Corporation belong to this series products.
D) maleic anhydride analog copolymer.Maleic anhydride has another name called MALEIC ANHYDRIDE, and it is used as there is unique position in the extended familys of monomer at synthesis pour point depressant.As added Long Chain Alkyl Acrylate maleic anhydride high fatty amine terpolymer, addition is that 0.06% (massfraction) can make the CFPP of spacious diesel oil reduce by 5 DEG C ~ l0 DEG C 0 to add the low temperature flowability that phenylethylene-maleic anhydride high fatty alcohol or amine terpolymer also can improve diesel oil effectively; Add the esterification products of maleic anhydride, mixing alpha-olefin, vinyl acetate ester and cinnamic multipolymer, addition is that 0.07% (massfraction) can make the CFPP of 10# diesel oil decline about 9 DEG C; Add alpha-olefin anhydride aliphatic alcohol (mol ratio 1:1:2) terpolymer, add 0.06% (massfraction) and the CFPP of diesel oil (b.p.184 DEG C-398 DEG C) can be made to decline about 6 DEG C.
E) acrylic polymer.Esters of acrylic acid polymers is the more fluidity improver of kind, the result of use of this series products is relevant with lateral chain of ester group average carbon number with the composition of ester in polymkeric substance, when the composition of alkyl acrylate is to when in diesel oil, the composition of N PARAFFIN & HEAVY NORMAL PARAFFIN is similar, multipolymer is the most effective.As polyacrylic acid 14 ester has certain depression effeCt to diesel oil, polymethyl acrylic acid dodecyl because of the depression effeCt of ester to diesel oil (b.p.180 DEG C-400 DEG C) relatively good.
China starts the research to pour point depressant from the initial stage fifties, nineteen fifty-three builds first lubricating oil additive alkyl bitter edible plant (code name T801) of having gone into operation, it is through polycondensation by oxidized petroleum wax and AIC13, and then it is refining, steaming shop obtains, but in reaction process, generates a considerable amount of indissoluble waste residue and yield is reduced.The sixties, China put into production Polymethacrylate type pour point depressant (code name T602).Meanwhile China starts the research to diesel pour inhibitor, and Dalian Petrochemical Industry Company starts to manufacture experimently diesel pour inhibitor.The seventies, China developed a kind of novel light pour point depressant polyalphaolefin (code name T803).It adopts soft wax cracking olefin to be raw material, and be polymerized under Zie-gler/Natta catalyzer exists through suitably refining, by hydrogen Molecular regulator amount, then wash Removal of catalyst by esterification water, in raw material olefin, alhpa olefin transformation efficiency reaches more than 90%.Meanwhile, the exploitation of diesel pour inhibitor also accelerates paces, and petrochemical complex academy of sciences absorbs the external technology with application diesel pour inhibitor of producing, and under the leader of refinery company of front petroleum department, is combined with each refinery.Carried out comprehensively add agent diesel oil apply work.At present, diesel pour inhibitor project team of Lanzhou Physical and Chemical Inst. cooperates with Lanzhou Chemical Industry Co., Ltd., China Petrochemical Corp, has built and has had 2500t efficient diesel pour point depression production line and compositional apparatus.
Current domestic conventional diesel pour inhibitor is T1804, but T1804 to high-content wax diesel oil to fall cold filter clogging temperature effect comparatively limited, cost is higher simultaneously.
Summary of the invention
The present invention improves the diesel pour inhibitor of background technology, proposes a kind of novel diesel pour inhibitor.Novel diesel pour point depressant can reduce costs, and improves and falls cold filter clogging temperature effect.
Technical solution of the present invention is: a kind of novel diesel pour point depressant, this improving agent forms by polyvinyl ester vinyl acetate (T1804), hexadecyl metrhacrylate maleic anhydride alpha-olefin copolymer, toluene three kinds of compositions are composite when 50-60 DEG C, and wherein polyvinyl ester vinyl acetate (T1804) is 50-60%, hexadecyl metrhacrylate-maleic anhydride alpha-olefin copolymer is 20-30%, toluene is 15-20%.
Described hexadecyl metrhacrylate-maleic anhydride-alpha-olefin (SMA-MA-α) multipolymer has following structure:
In formula, R1 is hexadecyl, and R2 is ClQ-C16 alkyl, and x is the molar percentage of methacrylic acid 16 ester in molecule, and y is the molar percentage of maleic anhydride in molecule, and Z is the molar percentage that α alkene is blamed, and X Y Z is 3:1:1 ~ 3:2:1.
Described hexadecyl metrhacrylate maleic anhydride alpha-olefin (SMA-MA α) multipolymer is prepared by the following method; with hexadecyl metrhacrylate (SMA), maleic anhydride (MA), alpha-olefin for raw material; take toluene as solvent; temperature of reaction is 80 ~ 100 DEG C; logical nitrogen protection; to the catalyzer benzoyl peroxide of solution dropwise reaction thing gross weight 1% ~ 3% under agitation condition; in 4 ~ 6 hours reaction times, obtain hexadecyl metrhacrylate-maleic anhydride-alpha-olefin (SMA-MA mono-α) multipolymer.
The mol ratio that hexadecyl metrhacrylate (SMA), maleic anhydride (MA) and α-alkene is blamed is 3:1:1 ~ 3:2:10
Novel diesel pour inhibitor prepared by the present invention can be applicable in the diesel oil of cycloalkyl, paraffinic crude refining, hexadecyl metrhacrylate-maleic anhydride-alpha-olefin (SMA-MA-α) and polyvinyl ester vinyl acetate (T1804) have good synergy, effectively reduce the cold filter clogging temperature of diesel oil.
Embodiment
Content for a better understanding of the present invention, is described further below in conjunction with specific embodiment, but is not limited to this.
Embodiment 1: the preparation of the polycomponent compound of polyvinyl ester vinyl acetate (T1804), SMA-MA-α multipolymer, toluene
60g polyvinyl ester vinyl acetate (T1804) is added in the there-necked flask that thermometer, constant speed whipping appts be housed, after 15g toluene heating in water bath to 50 DEG C, add 25g methacrylic acid 16 ester maleic anhydride alhpa olefin (SMA-MA-α) multipolymer, moderate-speed mixer 30min, terminates during homogeneous phase liquid in compound in flask.
Embodiment 2: the preparation of main ingredient SMA-MA-α multipolymer in compound
To thermometer is housed, prolong, the four-hole boiling flask of dropping funnel and constant speed whipping appts adds 28g hexadecyl metrhacrylate (SMA), 3g maleic anhydride (MA), 6g alpha-olefin, add 20ml toluene again, logical nitrogen protection, 60 DEG C are warming up under agitation condition, make reactants dissolved, competent 0.4g catalyzer benzoyl peroxide first field first again, after fully dissolving with 20ml toluene, add dropping funnel to hold with o when temperature rises to 80-100 DEG C, start to drip catalyzer at a slow speed, sustained reaction 5 hours under agitation condition, obtain hexadecyl metrhacrylate-maleic anhydride-alpha-olefin (SMA-MA-α) multipolymer.
Embodiment 3: the preparation of main ingredient SMA-MA-α multipolymer in compound
28g hexadecyl metrhacrylate (SMA), 3g maleic anhydride (MA), 6g alpha-olefin is added to the four-hole boiling flask that thermometer, prolong, dropping funnel and constant speed whipping appts are housed; add 20ml toluene again; logical nitrogen protection; 60 DEG C are warming up under agitation condition; make reactants dissolved; competent 0.8g catalyzer benzoyl peroxide first field first, after fully dissolving, adds dropping funnel and holds use with 20ml toluene again.When temperature rises to 80-100 DEG C, start to drip catalyzer at a slow speed, sustained reaction 5 hours under agitation condition, obtain hexadecyl metrhacrylate-maleic anhydride-alpha-olefin (SMA-MA-α) multipolymer.
Claims (3)
1. a novel diesel pour point depressant, it is characterized in that: this improving agent forms by polyvinyl ester vinyl acetate (T1804), hexadecyl metrhacrylate-maleic anhydride-alpha-olefin (SMA-MA-α) multipolymer and toluene three kinds of compositions are composite when 50-60 DEG C, wherein polyvinyl ester vinyl acetate (T1804) is 50-60%, hexadecyl metrhacrylate maleic anhydride-alpha-olefin (SMA-MA-α) multipolymer is 20-30%, toluene is 15-20%.
2. novel diesel pour point depressant as claimed in claim 1, is characterized in that: described hexadecyl metrhacrylate toxilic acid-α-alkene; Strange (SMA-MA-α) multipolymer has following structure:
R in formula
1for hexadecyl, R
2for C
l0-C
16alkyl, x is the mol ratio of hexadecyl metrhacrylate in molecule, and y is the mol ratio of maleic anhydride in molecule, and z is the mol ratio that α alkene is blamed, and X Y Z is 3:1:1 ~ 3:2:10.
3. novel diesel pour point depressant as claimed in claim 1 or 2, it is characterized in that: described hexadecyl metrhacrylate maleic anhydride alpha-olefin (SMA-MA-α) multipolymer is prepared by the following method, with methacrylic acid 16 ester (SMA), maleic anhydride (MA), alpha-olefin is raw material, take toluene as solvent, temperature of reaction is 80 ~ 100 DEG C, logical nitrogen protection, to the catalyzer benzoyl peroxide of solution dropwise reaction thing gross weight 1% ~ 3% under agitation condition, 4 ~ 6 hours reaction times, obtain hexadecyl metrhacrylate-maleic anhydride-alpha-olefin (SMA-MA-α) multipolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310651582.5A CN104694181A (en) | 2013-12-05 | 2013-12-05 | Novel diesel oil pour-point depressant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310651582.5A CN104694181A (en) | 2013-12-05 | 2013-12-05 | Novel diesel oil pour-point depressant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104694181A true CN104694181A (en) | 2015-06-10 |
Family
ID=53341744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310651582.5A Pending CN104694181A (en) | 2013-12-05 | 2013-12-05 | Novel diesel oil pour-point depressant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104694181A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN116120497A (en) * | 2022-12-27 | 2023-05-16 | 浙江工业大学 | Crude oil pour point depressant and preparation method thereof |
-
2013
- 2013-12-05 CN CN201310651582.5A patent/CN104694181A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN116120497A (en) * | 2022-12-27 | 2023-05-16 | 浙江工业大学 | Crude oil pour point depressant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Effect of polymeric cold flow improvers on flow properties of biodiesel from waste cooking oil | |
| CN102510878B (en) | Improve the composition of oil fuel cold flow properties | |
| CN102559302B (en) | Diesel pour point depressant and preparation method thereof | |
| US6403745B1 (en) | Gradient copolymers, as well as a method for their preparation and their use | |
| MXPA02005368A (en) | Copolymers which can be obtained using atrp methods, and method for producing and using the same. | |
| CA2789034C (en) | A composition having improved filterability | |
| CN105387347B (en) | A kind of crude oil pour-point depressant and preparation method thereof | |
| JP6516791B2 (en) | Functionalized diblock copolymer and method for producing the same | |
| CN105524211B (en) | A kind of preparation method of quadripolymer diesel pour inhibitor | |
| CN103184043A (en) | Crude oil pour point depressant and preparation method thereof | |
| CN102731739A (en) | Star polymer used as lubricating oil viscosity index improver, preparation method and application thereof | |
| CN106544067B (en) | The additive for fuel and oil comprising functionalization diblock copolymer | |
| CN102382695A (en) | Novel diesel oil pour point depressant | |
| JP2012521473A (en) | Low molecular weight (meth) acrylic polymer that does not contain a sulfur-containing compound, metal compound and halogen compound and has a small amount of residual monomer, a method for producing the (meth) acrylic polymer, and the (meth) acrylic polymer Use of | |
| CN101812348A (en) | Diesel pour point depressant | |
| JP5259901B2 (en) | Block copolymer and its production method and use | |
| CN108456279B (en) | Crude oil pour point depressant, and preparation method and application thereof | |
| CN104694181A (en) | Novel diesel oil pour-point depressant | |
| JPH0345693A (en) | Additive for diesel fuel | |
| TW201037072A (en) | Fuel compositions with improved cloud point and improved storage properties | |
| KR101176344B1 (en) | flow improver compositions at low temperature for fuel oil having bio-diesel and flow improver using the same | |
| CN104710560B (en) | A kind of dicyclopentadiene and Long Chain Alkyl Acrylate polymer pour point depressant for crude oil | |
| CN101608139A (en) | A kind of copolymer type low temperature flow improver for diesel fuel with rigid structure | |
| CN102477318A (en) | Biodiesel pour-point depressant, its preparation method and application | |
| CN107189831A (en) | A kind of alcoholysis type ter-polymers diesel pour inhibitor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150610 |