CN1175614A - Pour point reducer for high pour point crude oil - Google Patents
Pour point reducer for high pour point crude oil Download PDFInfo
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- CN1175614A CN1175614A CN 96115577 CN96115577A CN1175614A CN 1175614 A CN1175614 A CN 1175614A CN 96115577 CN96115577 CN 96115577 CN 96115577 A CN96115577 A CN 96115577A CN 1175614 A CN1175614 A CN 1175614A
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- pour point
- crude oil
- point depressant
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
A pour depressor suitable for high-solidifying-point (40-67 deg.C) crude oil containing wax (30-51%) is prepared from macro-molecular copolymer, which may be obtained by copolymerization of the C16-24 ester of unsaturated acid (or C16-24 alpha-olifine) with other unsaturates, and surfactant, which may be cationic or anionic one such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate and hexadecanetrimethyl quaternary ammonium bromide, in a ratio of 1:50-150. Said pour depressor can reduce the solidifing point of crude oil by 12 deg. C if it is poured into crude oil at 120 deg. C to treat the crude oil for 10 min.
Description
The present invention relates to a kind of synthetic method and application of pour point depressant.Because pour point depressant is to the highly selective of crude oil, this pour point depressant is fit to the high content of wax (30～51%), and the crude oil of high-solidification point (40～67 ℃) uses.
Solving the exploitation of crude oil with high solidifying point and carrying mainly is to rely on heating viscosity reduction, the method for O/w emulsion and pour point depressant.Heating viscosity reduction method fuel consumption is too big, and the O/w emulsion rule causes dehydration problem, and the method for pour point depressant is easy and simple to handle, no aftertreatment, the favor of current extremely oil field.But because pour point depressant is very strong to the crude oil specific aim, bibliographical information is to the pour point depressant effect that the high content of wax (30～51%) high-solidification point (40～67 ℃) crude oil uses all not good (Song welcome etc., oilfield chemistry, 1995, VOL.12, NO.2,185).
The purpose of this invention is to provide a kind of pour point depressant and select the suitable applications condition to make above-mentioned crude oil with high solidifying point depression of the freezing point.
Pour point depressant provided by the invention is the compound of a kind of high-molecular copolymer and tensio-active agent.This high-molecular copolymer is unsaturated acid C
16-24Ester or C
16-24The multipolymer of alhpa olefin and other unsaturated organic compounds.Unsaturated acid C
16-24The ester of alcohol is various unsaturated acid such as vinylformic acid, maleic acid, FUMARIC ACID TECH GRADE etc. and C
16-24The esterification products of alcohol, other unsaturatess are vinyl acetate between to for plastic, vinylbenzene, maleic acid, FUMARIC ACID TECH GRADE etc.Feature of the present invention is: unsaturated acid C in the high-molecular copolymer
16-24Ester or C
16-24Alhpa olefin and other unsaturated compound proportionings are 1/1～20/1, are the best with 1/1～5/1 wherein, and high molecular nonpolar long-chain side chain C number has certain proportion to distribute at 16～25, and polar side chain C number is less than 5; Tensio-active agent is an ionogenic surfactant, and special anionic or cationic surfactant can not only disperse and solubilising paraffin, and itself have pour-point depressing process; Aniorfic surfactant can be selected alkyl sodium sulfonate or sodium alkyl sulfate such as sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium stearyl sulfate for use; Cats product can be selected cetyl trimethyl quaternary ammonium bromides etc. for use.High-molecular copolymer is 1: 50～150 (weight) with the ratio that cooperates of tensio-active agent in the pour point depressant, and preferable cooperation ratio is 1: 80～110.
Treatment temp and treatment time are remarkable to the pour point depression of crude oil influential effect when application conditions of pour point depressant such as the injection rate of pour point depressant, pour point depressant injection crude oil, treatment temp generally makes it to mix being higher than under 10～20 ℃ of temperature of former oil freezing point pour point depressant added, and preferable temperature ranges is 80～120 ℃; Treatment time should be no less than 2 minutes, and to guarantee pour point depressant and crude oil thorough mixing, the general treatment time is 2～15 minutes; The addition of pour point depressant can reduce temperature and decides according to actual needs, but it is too much to add the amount of pour point depressant, will improve the cost of crude oil, general add-on be crude oil heavy 0.05～2%, can make former oil freezing point fall 8～11 ℃; Under the best applications condition, pour point depressant provided by the invention can make depression of the freezing point 12 ℃ of crude oil.
The preparation method of crude oil with high solidifying point pour point depressant of the present invention can press step:
1. synthetic macromolecule multipolymer
Use unsaturated acid C
16-24Ester or C
16-24Alhpa olefin and unsaturated macromolecular compound generation copolyreaction synthetic copolymer, reaction technology is routinely carried out.
2. preparation pour point depressant
To go up the synthetic multipolymer mixes with ionogenic surfactant and can be mixed with pour point depressant.
Below by example pour point depressant provided by the invention is described further.
Synthesizing of example 1 high-molecular copolymer
In two mouthfuls of reaction flasks of 50ml, add vinylformic acid C successively
16-24Ester 7.4g, vinyl acetate between to for plastic 2.2g makes the benzene 14.4g of solvent, heating makes reactants dissolved, adds the Diisopropyl azodicarboxylate 0.096g as initiator then, 80 ℃ of temperature of reaction, backflow 8hr gets solvent-laden high-molecular copolymer, and this multipolymer does not influence its use.Also can after back flow reaction, continue heating (80 ℃), separated from solvent is gone out, get vinylformic acid C
16-24Ester-acetate ethylene copolymer.
The preparation of example 2 pour point depressants
Example 1 is made multipolymer, press the pure block copolymer amount and calculate, add 100 times Sodium dodecylbenzene sulfonate, thorough mixing promptly is mixed with pour point depressant of the present invention.
Embodiment 3 injects Shenyang crude oil (content of wax 30～51%, zero pour 40～67%) with example 1 described high-molecular copolymer under differing temps, former oil freezing point result of variations sees Table 1.
The influence that table 1 high-molecular copolymer changes former oil freezing point
| Treatment temp ℃ former oil freezing point ℃ reduction value ℃ |
| ????80????????????42??????????????6 ????90????????????41??????????????7 ????100???????????41??????????????7 ????110???????????40??????????????8 ????120???????????39??????????????9 |
The multipolymer amount is 100ppm, treatment time 10min.
Example 4 injects the Shenyang crude oil with Sodium dodecylbenzene sulfonate under differing temps, former oil freezing point result of variations sees Table 2.
The influence that table 2 tensio-active agent changes former oil freezing point
| Treatment temp ℃ former oil freezing point ℃ reduction value ℃ |
| ????80????????????42??????????????6 ????90????????????42??????????????6 ????100???????????41??????????????7 ????110???????????41??????????????7 ????120???????????40??????????????8 |
Tensio-active agent injection rate 10000ppm, treatment time 10min.
Example 5 will inject the Shenyang crude oil by the pour point depressant of example 1,2 described method preparation under differing temps, former oil freezing point result of variations sees Table 3.
The influence that table 3 pour point depressant changes former oil freezing point
| Treatment temp ℃ former oil freezing point ℃ reduction value ℃ |
| ????80????????????40??????????????8 ????90????????????40??????????????8 ????100???????????39??????????????9 ????110???????????37??????????????11 ????120???????????36??????????????12 ????126???????????36??????????????12 |
By the multipolymer injection rate is 100ppm, Sodium dodecylbenzene sulfonate injection rate 10000ppm, treatment time 10min.
By above-mentioned example, utilize pour point depressant provided by the invention can make the depression of the freezing point of crude oil with high solidifying point reach 12 ℃, and the synthetic method of this pour point depressant is simple, easy to use, be suitable for using.
Claims (4)
1. the pour point depressant of a crude oil with high solidifying point is characterized in that it being high-molecular copolymer and the tensio-active agent compound by 1: 50～150 weight ratio mixed preparing, and so-called high-molecular copolymer is unsaturated acid C
16-24Ester or C
16-24Alhpa olefin and unsaturated organic compound carry out copolyreaction and make, and tensio-active agent is meant ionogenic surfactant.
2. according to the described pour point depressant of claim 1, it is characterized in that unsaturated acid C in the high-molecular copolymer therein
16-24Ester or C
16-24Alhpa olefin and unsaturated organic compound proportioning are 1～20: 1.
3. according to the described pour point depressant of claim 1, it is characterized in that unsaturated acid C
16-24Ester is vinylformic acid, maleic acid or FUMARIC ACID TECH GRADE and C
16-24The esterification products of alcohol, other unsaturated organic compounds are vinyl acetate between to for plastic, vinylbenzene, maleic acid or FUMARIC ACID TECH GRADE.
4. according to the described pour point depressant of claim 1, it is characterized in that tensio-active agent is cationic or the surperficial tensio-active agent sodium lauryl sulphate of anionic, Sodium dodecylbenzene sulfonate, sodium stearyl sulfate, cetyl trimethyl quaternary ammonium bromides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115577 CN1074037C (en) | 1996-09-04 | 1996-09-04 | Pour point reducer for high pour point crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115577 CN1074037C (en) | 1996-09-04 | 1996-09-04 | Pour point reducer for high pour point crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175614A true CN1175614A (en) | 1998-03-11 |
| CN1074037C CN1074037C (en) | 2001-10-31 |
Family
ID=5122813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96115577 Expired - Fee Related CN1074037C (en) | 1996-09-04 | 1996-09-04 | Pour point reducer for high pour point crude oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1074037C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001096503A2 (en) * | 2000-06-15 | 2001-12-20 | Clariant International Ltd | Additives for improving the cold flow properties and the storage stability of crude oil |
| CN1302085C (en) * | 2005-03-25 | 2007-02-28 | 山东大学 | Multifunctional |
| CN101712787B (en) * | 2008-10-08 | 2012-01-11 | 中国石油天然气集团公司 | Sulfonic acid-containing organic macromolecule reaction type crude oil flow modifying agent |
| CN104694106A (en) * | 2015-03-05 | 2015-06-10 | 黑龙江信维源化工有限公司 | Sulfonate surfactant suitable for weak-alkali ternary compound oil displacement and application of sulfonate surfactant |
| CN104710560A (en) * | 2013-12-13 | 2015-06-17 | 中国石油天然气集团公司 | Dicyclopentadiene and acrylic acid high-carbon alcohol ester polymer crude oil pour point depressant |
| CN105524216A (en) * | 2015-11-04 | 2016-04-27 | 宁波市蓝润能源科技有限公司 | Environment-friendly pour-point depressant and preparation method thereof |
| CN106468396A (en) * | 2016-08-28 | 2017-03-01 | 山东成泰化工有限公司 | A kind of petroleum pour depressant of hexahydro-phthalic acid two high-carbon alcohol ester |
| CN106811187A (en) * | 2017-01-20 | 2017-06-09 | 中国石油大学(华东) | Pour point depressant for crude oil and preparation method thereof |
| CN108409910A (en) * | 2018-04-16 | 2018-08-17 | 青岛大学 | A kind of acrylic ester grafted type alcoholysis EVA pour point depressant for crude oil and preparation method thereof |
| CN108456279A (en) * | 2018-04-26 | 2018-08-28 | 杨冰川 | A kind of pour point depressant for crude oil and the preparation method and application thereof |
-
1996
- 1996-09-04 CN CN 96115577 patent/CN1074037C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001096503A3 (en) * | 2000-06-15 | 2003-01-09 | Clariant Int Ltd | Additives for improving the cold flow properties and the storage stability of crude oil |
| US6821933B2 (en) | 2000-06-15 | 2004-11-23 | Clariant International Ltd. | Additives for improving the cold flow properties and the storage stability of crude oil |
| WO2001096503A2 (en) * | 2000-06-15 | 2001-12-20 | Clariant International Ltd | Additives for improving the cold flow properties and the storage stability of crude oil |
| CN1302085C (en) * | 2005-03-25 | 2007-02-28 | 山东大学 | Multifunctional |
| CN101712787B (en) * | 2008-10-08 | 2012-01-11 | 中国石油天然气集团公司 | Sulfonic acid-containing organic macromolecule reaction type crude oil flow modifying agent |
| CN104710560A (en) * | 2013-12-13 | 2015-06-17 | 中国石油天然气集团公司 | Dicyclopentadiene and acrylic acid high-carbon alcohol ester polymer crude oil pour point depressant |
| CN104694106A (en) * | 2015-03-05 | 2015-06-10 | 黑龙江信维源化工有限公司 | Sulfonate surfactant suitable for weak-alkali ternary compound oil displacement and application of sulfonate surfactant |
| CN105524216B (en) * | 2015-11-04 | 2018-01-26 | 宁波蓝润能源科技股份有限公司 | A kind of environment-friendly type pour-point depressant and preparation method thereof |
| CN105524216A (en) * | 2015-11-04 | 2016-04-27 | 宁波市蓝润能源科技有限公司 | Environment-friendly pour-point depressant and preparation method thereof |
| CN106468396A (en) * | 2016-08-28 | 2017-03-01 | 山东成泰化工有限公司 | A kind of petroleum pour depressant of hexahydro-phthalic acid two high-carbon alcohol ester |
| CN106811187A (en) * | 2017-01-20 | 2017-06-09 | 中国石油大学(华东) | Pour point depressant for crude oil and preparation method thereof |
| CN106811187B (en) * | 2017-01-20 | 2019-08-30 | 中国石油大学(华东) | Pour point depressant for crude oil and preparation method thereof |
| CN108409910A (en) * | 2018-04-16 | 2018-08-17 | 青岛大学 | A kind of acrylic ester grafted type alcoholysis EVA pour point depressant for crude oil and preparation method thereof |
| CN108409910B (en) * | 2018-04-16 | 2022-04-22 | 青岛大学 | Acrylate grafted alcoholysis EVA (ethylene-vinyl acetate) crude oil pour point depressant and preparation method thereof |
| CN108456279A (en) * | 2018-04-26 | 2018-08-28 | 杨冰川 | A kind of pour point depressant for crude oil and the preparation method and application thereof |
| CN108456279B (en) * | 2018-04-26 | 2020-03-31 | 杨冰川 | Crude oil pour point depressant, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1074037C (en) | 2001-10-31 |
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