CN102872750B - Residual oil sulfonation method - Google Patents
Residual oil sulfonation method Download PDFInfo
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- CN102872750B CN102872750B CN201210384390.8A CN201210384390A CN102872750B CN 102872750 B CN102872750 B CN 102872750B CN 201210384390 A CN201210384390 A CN 201210384390A CN 102872750 B CN102872750 B CN 102872750B
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Abstract
The invention relates to a method for sulfonating residual oil to prepare sulphosalts surfactants used by oil fields and provides a residual oil sulfonation method which solves the problems of carbonization and coking in the residual oil sulfonation process. The residual oil sulfonation method is characterized in that residual oil and solvents are diluted in mass ratio of 1:(2-5) and are cooled, sulfonating agents and the solvents are diluted in mass ratio of 1:(1-3), relative residual oil of the diluted solutions is filled into 1/2-1/20 complexing agents, the complexing agents are filled into the residual oil and subjected to ageing for 0.5-2h, diluted sulfonating agents with mass to be 1-3 times that of the residual oil are gradually added, then alkali is added for neutralization, bottom water solutions are settled and removed, the solvents are removed through distillation, and finally petroleum sulfonate products can be obtained. By adopting the technical scheme, sufficient utilization of residual oil is achieved, the problems of carbonization and coking in the residual oil sulfonation process are solved, requirements for the sulfonating process is low, and residual oil sulfonating can be carried out without changing the liquid-phase sulfonating process condition.
Description
Technical field
The present invention relates to residual oil to carry out the method that oil field sulfonate surfactant is prepared in sulfonation, especially a kind of residual oil method of sulfonating.
Background technology
Petroleum sulfonate is the oil field oil displacement agent product of producing take 260 ℃～500 ℃ fractional oil of crude oil as raw material substantially, for being greater than 500 ℃ of above residue fractions, because its condensation point is high, viscosity is large, in sulfonation process, be easy to occur the problem such as carbonization, coking, be generally difficult to as the raw material of producing petroleum sulfonate.Oil from Shengli oil field is heavier, and the residual oil content after distillation is especially up to more than 50%.Residual oil is mainly made up of colloid, asphalitine, condensed-nuclei aromatics and fractional saturation hydrocarbon, and its molecular weight is large, can sulfonation component high, still can be for aspects such as tertiary oil production in oil field, drilling well, thickened oil recoveries after oversulfonate.Therefore, realize residual oil sulfonation and can make full use of raw material resources, produce effective oil field chemical products.At present, for residual oil sulfonation, there are no relevant report, this patent is own original creation technology.
Summary of the invention
Object of the present invention is just to provide a kind of method of residual oil sulfonation production anion surfactant, through adding complexing agent to reduce sulfonating reaction speed, sulfonating reaction is carried out by different level, thereby carbonization, coking problem in residual oil sulfonation process are overcome, and effectively control the extent of reaction, obtain a kind of residual oil method of sulfonating of the mahogany acid product salt needing.Technical scheme is: residual oil method of sulfonating is the process of residual oil sulfonation production anion surfactant, is through adding complexing agent to reduce sulfonating reaction speed, sulfonating reaction is carried out by different level, obtaining mahogany acid product salt.Described residual oil method of sulfonating is first by residual oil and solvent 1: 2 in mass ratio～5 dilutions, then be cooled to 0 ℃～50 ℃, after 1: 1 in mass ratio～3 dilutions of sulfonating agent and solvent, get its relative residual oil quality 1～3 times, add again after 1/2～1/20 complexing agent, add gradually in cooling residual oil, add rear aging 0.5～2h, then add gradually sulfonating agent after the dilution of 1～3 times of residual oil quality, in sulfonating agent adition process, maintain the temperature at 10 ℃～50 ℃, then aging 0.5～5h under 20 ℃～60 ℃ conditions of temperature, add alkali to neutralize, sedimentation removes bottom water solution, distillation is except desolventizing, finally can obtain mahogany acid product salt.Described solvent is dichloroethanes; Sulfonating agent is SO
3; Complexing agent is dimethyl carbonate; Alkali is ammoniacal liquor or sodium hydroxide solution.Adopt after technique scheme, 1, realized making full use of of residual oil, produce and adapt to the multi-purpose chemical products in oil field; 2, overcome carbonization, the coking problem in residual oil sulfonating reaction process, and can control the extent of reaction, the sulfonate product of production requirement according to sulfonation temperature and sulfonating agent consumption etc.; 3, low to process for sulfonation requirement, can under the condition that does not change liquid phase process for sulfonation, carry out residual oil sulfonation.
The specific embodiment
Embodiment 1
Get 80g residual oil and 320g dichloroethanes and mix, then residual oil is cooled to 20 ℃.SO
3with dichloroethanes dilution be the solution of mass percent 25%, get 80g and add 20g dimethyl carbonate, after mixing, join gradually in above-mentioned cooling residual oil solution, remain on 20 ℃ add after, continue to stir 0.5h under 20 ℃ of conditions.Then get mass percent and be 25% SO
3solution 240g, add gradually in the residual oil solution after above-mentioned sulfonation, in adition process, make reaction temperature continue to remain on 20 ℃, add completely, under 30 ℃ of conditions, stir 1h, then add 23% ammoniacal liquor to neutralize, carry out sedimentation at 70 ℃, separate lower aqueous solution, product evaporation in upper strata, except desolventizing, is obtained to sulfonate product.
Embodiment 2
Get 80g residual oil and 320g dichloroethanes and mix, then residual oil is cooled to 20 ℃.SO
3with dichloroethanes dilution be the solution of mass percent 25%, get 100g and add 20g dimethyl carbonate, after mixing, join gradually in above-mentioned cooling residual oil solution, remain on 20 ℃ add after, continue to stir 0.5h under 20 ℃ of conditions.Then get mass percent and be 25% SO
3solution 220g, add gradually in the residual oil solution after above-mentioned sulfonation, in adition process, make reaction temperature continue to remain on 20 ℃, add completely, under 30 ℃ of conditions, stir 1h, then add 23% ammoniacal liquor to neutralize, carry out sedimentation at 70 ℃, separate lower aqueous solution, product evaporation in upper strata, except desolventizing, is obtained to sulfonate product.
Embodiment 3
Get 80g residual oil and 320g dichloroethanes and mix, then residual oil is cooled to 20 ℃.SO3 is the solution of mass percent 25% with dichloroethanes dilution, gets 120g and adds 20g dimethyl carbonate, joins gradually in above-mentioned cooling residual oil solution after mixing, remain on 20 ℃ add after, continue to stir 1h under 20 ℃ of conditions.Then get mass percent and be 25% SO
3solution 200g, add gradually in the residual oil solution after above-mentioned sulfonation, in adition process, make reaction temperature continue to remain on 20 ℃, add completely, under 30 ℃ of conditions, stir 1h, then add 23% ammoniacal liquor to neutralize, carry out sedimentation at 70 ℃, separate lower aqueous solution, product evaporation in upper strata, except desolventizing, is obtained to sulfonate product.
Embodiment 4
Get 80g residual oil and 320g dichloroethanes and mix, then residual oil is cooled to 10 ℃.SO
3with dichloroethanes dilution be the solution of mass percent 25%, get 200g and add 20g dimethyl carbonate, after mixing, join gradually in above-mentioned cooling residual oil solution, remain on 10 ℃ add after, continue to stir 1h under 10 ℃ of conditions.Then get mass percent and be 25% SO
3solution 120g, add gradually in the residual oil solution after above-mentioned sulfonation, in adition process, make reaction temperature continue to remain on 10 ℃, add completely, under 50 ℃ of conditions, stir 1h, then add 23% ammoniacal liquor to neutralize, carry out sedimentation at 70 ℃, separate lower aqueous solution, product evaporation in upper strata, except desolventizing, is obtained to sulfonate product.
Claims (1)
1. a residual oil method of sulfonating, is characterized in that: get 80g residual oil and 320g dichloroethanes and mix, then residual oil is cooled to 20 ℃; SO
3with dichloroethanes dilution be the solution of mass percent 25%, get 80g and add 20g dimethyl carbonate, after mixing, join gradually in above-mentioned cooling residual oil solution, remain on 20 ℃ add after, continue to stir 0.5h under 20 ℃ of conditions; Then get mass percent and be 25% SO
3solution 240g, add gradually in the residual oil solution after above-mentioned sulfonation, in adition process, make reaction temperature continue to remain on 20 ℃, add completely, under 30 ℃ of conditions, stir 1h, then add 23% ammoniacal liquor to neutralize, carry out sedimentation at 70 ℃, separate lower aqueous solution, product evaporation in upper strata, except desolventizing, is obtained to sulfonate product.
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| CN105062652B (en) * | 2015-08-21 | 2017-09-05 | 太原理工大学 | A kind of method of water-coal-slurry surfactant is produced from waste lubricating oil |
| CN106810471B (en) * | 2015-12-01 | 2018-09-04 | 中国石油天然气股份有限公司 | A kind of production method of petroleum sulfonate |
| CN108251088B (en) * | 2017-12-20 | 2020-05-08 | 中国石油天然气股份有限公司 | Sulfonated residual oil modified bentonite foam stabilizer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556792A (en) * | 2001-09-22 | 2004-12-22 | �����ѧ��˾ŷ�ֹ�˾ | Sulphonation of phenols |
| CN102086164A (en) * | 2010-12-31 | 2011-06-08 | 黄石市美丰化工有限责任公司 | Preparation method of 2-hydroxy-4-methyoxy-benzophenone-5-sulfoacid |
| CN102190605A (en) * | 2010-03-03 | 2011-09-21 | 北京中石大节能科技发展有限责任公司 | Petroleum sulfonate anionic surfactant and preparation method thereof |
| CN102584643A (en) * | 2011-01-13 | 2012-07-18 | 中国石油大学(北京) | Crude oil vacuum residue fraction sulfonate and preparation method thereof |
| CN102643216A (en) * | 2012-04-01 | 2012-08-22 | 中国石油化工股份有限公司 | Method for preparing surfactant by using extracted oil alkylation product sulfonation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0645791B2 (en) * | 1986-01-17 | 1994-06-15 | 三菱油化株式会社 | Dispersant for water slurry of carbonaceous fine powder |
-
2012
- 2012-09-29 CN CN201210384390.8A patent/CN102872750B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556792A (en) * | 2001-09-22 | 2004-12-22 | �����ѧ��˾ŷ�ֹ�˾ | Sulphonation of phenols |
| CN102190605A (en) * | 2010-03-03 | 2011-09-21 | 北京中石大节能科技发展有限责任公司 | Petroleum sulfonate anionic surfactant and preparation method thereof |
| CN102086164A (en) * | 2010-12-31 | 2011-06-08 | 黄石市美丰化工有限责任公司 | Preparation method of 2-hydroxy-4-methyoxy-benzophenone-5-sulfoacid |
| CN102584643A (en) * | 2011-01-13 | 2012-07-18 | 中国石油大学(北京) | Crude oil vacuum residue fraction sulfonate and preparation method thereof |
| CN102643216A (en) * | 2012-04-01 | 2012-08-22 | 中国石油化工股份有限公司 | Method for preparing surfactant by using extracted oil alkylation product sulfonation method |
Non-Patent Citations (1)
| Title |
|---|
| JP昭62-168530A 1987.07.24 |
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Effective date of registration: 20171222 Address after: 257000 Dongying Port Economic Development Zone, Dongying, Shandong Patentee after: Shandong Daming Fine Chemical Co., Ltd. Address before: No. 27, Zoucheng Road, Shengli Industrial Park, Dongying, Shandong Patentee before: Zhongsheng Environmental Protection Co., Ltd. of Shengli Oilfield |
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