CN1468849A - Prepn of faintly alkaline alkylbenzene sulfonate - Google Patents
Prepn of faintly alkaline alkylbenzene sulfonate Download PDFInfo
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- CN1468849A CN1468849A CNA021407193A CN02140719A CN1468849A CN 1468849 A CN1468849 A CN 1468849A CN A021407193 A CNA021407193 A CN A021407193A CN 02140719 A CN02140719 A CN 02140719A CN 1468849 A CN1468849 A CN 1468849A
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- -1 alkylbenzene sulfonate Chemical class 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000006277 sulfonation reaction Methods 0.000 claims description 7
- 239000010779 crude oil Substances 0.000 claims description 5
- 229940077388 benzenesulfonate Drugs 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003849 aromatic solvent Substances 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002736 nonionic surfactant Substances 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract 1
- 239000002585 base Substances 0.000 description 15
- 239000013543 active substance Substances 0.000 description 10
- 238000006073 displacement reaction Methods 0.000 description 8
- 239000003027 oil sand Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation of faintly alkaline alkylbenzene sulfonate adopts heavy alkylbenzene through rectification and cutting treatment as main material, which is reacted with fuming sulfuric acid and SO3 gas or liquid. Through subsequent addition of technological water to hydrolyze, aging, addition of sodium hydroxide solution for neutralization and other steps, sodium alkylbenzene sulfonate is produced. Adding lower carbon alcohol, aromatic solvent or other solvent, and non-ionic surfactant can produce faintly alkaline alkylbenzene sulfonate surfactant.
Description
Technical field
The present invention relates to a kind of oil field (displacement of reservoir oil) and use tensio-active agent, relate in particular to a kind of preparation method of weak base alkylbenzene sulfonate.
Background technology
The application surface promoting agent recovers the oil to study in the theory and practice so far and has all obtained very big development in petro-technology.At present, following several injection systems have been formed basically.(1) active water drive; (2) micellar solution flooding; (3) the low interfacial tension system is recovered the oil; (4) ternary composite driving.Wherein ternary composite driving (alkali+polymkeric substance+tensio-active agent) still can obtain higher oil displacement efficiency under the situation of low surfactant consumption significantly, and therefore, it becomes the new technology in economic and technical raising recovery ratio that can both be successful.
After the oil field enters high water-cut stage, surplus oil with discontinuous oil clot by trap in the reservoir rocks hole, two main power that act on the oil droplet are adhesive tape power and capillary force.As use suitable surfactant system, reduce the interfacial tension between profit, just reduced the resistance that the oil droplet distortion is brought when using irreducible oil to move, thus oil displacement efficiency improved.
Present employed tensio-active agent generally is an alkylbenzene sulfonate, but contains highly basic such as sodium hydroxide or potassium hydroxide in this alkylbenzene sulfonate, during use, because its alkalescence is too strong, thereby as easy as rolling off a log to various device and pipeline generation corrosive nature.
Summary of the invention
Purpose of the present invention is to provide a kind of preparation method of weak base alkylbenzene sulfonate, the alkyl benzene sulphonate (ABS) saline alkali of this method preparation a little less than, can avoid and slow down injury to a great extent to equipment and oil reservoir.
For achieving the above object, preparation method provided by the invention comprises the steps:
1), rectifying cutting process
The raw material of the weak base alkylbenzene sulfonate that this invention is developed is a heavy alkyl benzene, and heavy alkyl benzene need carry out the rectifying cutting process before use, under the vacuum degree condition of 0.098Mpa, and tower top temperature 300-365 ℃.The raw material of this product comprises the crude oil fractions oil that adds 10-20wt% except that heavy alkyl benzene, crude oil fractions oil comprises and subtracts two, subtracts three, subtracts four line distillates or furfural extract oil.
2), sulfonation reaction
With raw material described above and concentration is the sulphur trioxide (SO of the oleum, 5% (volume percent) of 20% (weight percent)
3) the liquid SO of gas or 20% (weight percent)
3In molar ratio=1: the ratio of 1-1.6 was the best with 1: 1.4.This step can adopt still formula or pattern sulfonation reaction, and range of reaction temperature is 30-45 ℃, is the best with 35 ℃.Except that the pattern reaction is that the still reaction time is 3-10 hour, is the best with 6 hours the instantaneous reaction.Need to add the process water of 1-4% after sulfonation reaction finishes, be hydrolyzed 0.5-2 hour, the aging more same time.Need leave standstill branch acid in 6-8 hour when adopting the oleum sulfonation.
3), neutralization is composite
To in and add the sodium hydroxide solution of 20-40% in the still by volume, under 50-70 ℃, carry out neutralization reaction, stirs after 1-3 hour, to 7-9, obtain sodium alkyl benzene sulfonate with sodium hydroxide adjustment pH value.
The solvent of adding 10-30% and the nonionogenic tenside of 0-5% obtain weak base alkyl benzene sulfonate tensio-active agent in the above-mentioned product that makes.
Above-mentioned solvent comprises: the low-carbon alcohol of 3-8 carbon and aromatic solvent;
Above-mentioned ionic surfactant pack is drawn together: OP, NP and higher alcohols polyethenoxy ether class.
Description of drawings
Fig. 1 is Na in the weak base tensio-active agent of the present invention
2CO
3Concentration is to the influence of interfacial tension.
Fig. 2 is a weak base ternary system viscosity stability of the present invention.
Fig. 3 is the adsorption isothermal line of weak base tensio-active agent of the present invention on the grand celebration oil-sand.
Embodiment
Embodiment
Get the heavy alkyl benzene raw material of 300 grams through cutting process, be heated to 37 ℃ in the reactor of 1000ml, dropping contains 20% (weight percent) SO under stirring condition
3Oleum or be dissolved in liquid SO3 in the solvent, reacted 4 hours; Using the NaOH of 20% (weight percent) to be neutralized to the pH value then is 7, divide acid again or desolvate, obtain the heavy alkylbenzene sulfonate monomer, the twelve earthly branches alkyl group benzene that in monomer, adds 10% (weight percent) again, the polar solvent of the nonionogenic tenside and 20% (weight percent) of 0-5% (weight percent), promptly obtaining active matter content is the used for tertiary oil recovery weak base alkyl benzene sulfonate surfactant of 50% (weight percent).
Below be the conclusion that weak base alkylbenzene sulfonate of the present invention obtains by experiment:
1, interfacial tension performance evaluation
Consult Fig. 1, experiment conclusion shows that in the promoting agent (0.025-0.2wt%) and alkali (0.6-1.2wt%) concentration range of broad, weak base promoting agent ternary system can form ultra low interfacial tension with three factory's test site crude oil and reach 10
-3The mN/m order of magnitude even lower.
2, ternary system interfacial tension stability
Experimental result shows that in the present time range of investigating (95 days), also dynamic and equilibrium interfacial tension all shows satisfactory stability.
3, ternary system viscosity stability
See also Fig. 2, surfactant concentration is 0.2wt%, Na
2CO
3Concentration is 1.8wt%, when polymkeric substance (Chaoyang ultra-high molecular weight) concentration (effectively) is 1400mg/L, the viscosity of ternary system be 38.4mP.s (with NaOH concentration under the equal conditions be that the ternary system viscosity of 1.2wt% is suitable).Ternary system places that viscosity is 30.6mP.s after one month, and viscosity break ratio is 20%, and the ternary system viscosity table reveals stability preferably.
4, the isothermal mensuration of alkaline consumption
Na
2CO
3With the alkaline consumption rule accords with Langmuir law of NaOH on the grand celebration oil-sand, alkali consumption increases with the increase of equilibrium concentration, and when alkali concn was increased to certain value, alkaline consumption reached balance.Calculate Na by weight
2CO
3Close with the alkali consumption of NaOH on the grand celebration oil-sand; Calculate with equivalent, then the consumption of NaOH on the grand celebration oil-sand compares Na
2CO
3Exceed nearly 4 times.Illustrate that the strong NaOH of alkalescence and the effect of oil-sand are better than the relative weak Na of alkalescence
2CO
3, this point is highly beneficial to carrying out field test from now on.
5, the adsorption isothermal line of weak base tensio-active agent on the grand celebration oil-sand
See also Fig. 3, weak base surfactivity, ORS-41 and the B-100 adsorption isothermal line on the grand celebration oil-sand does not meet the Langmuir Adsorption law, has a maximum value, and this mainly is to exist micelle-forming concentration relevant with surfactant soln.Experimental result shows, the weak base tensio-active agent on the grand celebration oil-sand maximal absorptive capacity and equilibrium adsorption capacity a little less than ORS-41 and B-100.This provides foundation for the consumption that reduces tensio-active agent in the field test.
6, indoor oil displacement experiment
The indoor displacement of reservoir oil evaluation of weak base tensio-active agent has obtained PRELIMINARY RESULTS at present.Table 1 is artificial inhomogeneous (variation coefficient is 0.72) rock core oil displacement experiment result, and the result shows, selects suitable system slug and injection mode, and the comparable water drive of ternary composite driving oil displacement efficiency improves more than 20% (OOIP).
Table 1 oil displacement experiment is table as a result
| Sequence number | Gas is surveyed the rate (* 10 of oozing -3μ ? ??m 2) | Oil saturation (%) | Waterflood recovery efficiency factor (%) | Chemical flooding recovery ratio improvement value (%) | Overall recovery factor (%) |
| ????1 | ????1274 | ????74.4 | ????41.3 | ????25.6 | ????66.9 |
| ????2 | ????1225 | ????73.4 | ????41.8 | ????26.4 | ????68.2 |
| ????3 | ????1270 | ????76.4 | ????41.3 | ????29.7 | ????71.0 |
Injection mode: (A * 1.2%+S * 0.3%+P1400mg/L) * 0.3pv+P * 0.2pv
Rock core specification: 3.6 * 3.6 * 30cm
Claims (8)
1, a kind of preparation method of weak base alkylbenzene sulfonate is a main raw material with the heavy alkyl benzene, and its key step is as follows:
A), rectifying cutting process
Vacuum tightness 0.098Mpa, tower top temperature 300-365 ℃, the crude oil fractions oil of 10-20wt%;
B), sulfonation reaction
With the sulfur trioxide gas of above-mentioned raw materials and 5% (volume percent) in molar ratio=1: the ratio of 1-1.6 is reacted, range of reaction temperature 30-45 ℃, pattern reaction, the process water of adding 1-4% after reaction finishes, be hydrolyzed the aging more identical time 0.5-2 hour;
C), neutralization is composite
To in and still add the sodium hydroxide solution of 20-40% by volume, neutralize under 50-70 ℃, stirred 1-3 hour, to 7-9, obtain sodium alkyl benzene sulfonate with sodium hydroxide adjustment pH value.
2, preparation method as claimed in claim 1 is characterized in that, crude oil fractions oil is for subtracting two, subtract three, subtracting four line distillates or furfural extract oil among the described step a.
3, preparation method as claimed in claim 1 is characterized in that, sulfonation reaction adopts the sulfan of the oleum or 20% (weight percent) of 20% (weight percent) among the described step b.
4, as claim 1 or 3 described preparation methods, it is characterized in that, leave standstill branch acid in 6-8 hour when adopting the oleum sulfonation.
5, preparation method as claimed in claim 1 is characterized in that, the ratio of raw material and sulphur trioxide is 1: 1.4 among the described step b.
6, preparation method as claimed in claim 1 is characterized in that, temperature of reaction is 35 ℃ among the described step b.
7, preparation method as claimed in claim 1 is characterized in that, is still reaction among the described step b, and the reaction times is 3-10 hour.
8, preparation method as claimed in claim 6 is characterized in that, the described reaction times is 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02140719.3A CN1193985C (en) | 2002-07-15 | 2002-07-15 | Prepn of faintly alkaline alkylbenzene sulfonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02140719.3A CN1193985C (en) | 2002-07-15 | 2002-07-15 | Prepn of faintly alkaline alkylbenzene sulfonate |
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| Publication Number | Publication Date |
|---|---|
| CN1468849A true CN1468849A (en) | 2004-01-21 |
| CN1193985C CN1193985C (en) | 2005-03-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02140719.3A Expired - Lifetime CN1193985C (en) | 2002-07-15 | 2002-07-15 | Prepn of faintly alkaline alkylbenzene sulfonate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604670A (en) * | 2012-02-10 | 2012-07-25 | 胜利油田中胜环保有限公司 | Method for preparing raw material of oil sulfonate for displacing oil in oilfield |
| CN105670590A (en) * | 2015-12-31 | 2016-06-15 | 中国石油天然气股份有限公司 | Ternary composite system and surfactant suitable for high-temperature hypersalinity oil reservoir and preparation method of ternary composite system and surfactant |
| CN107827784A (en) * | 2017-10-30 | 2018-03-23 | 苏州市浒墅关化工添加剂有限公司 | A kind of preparation method of sodium heavy alkyl benzene sulfonate |
| CN110938022A (en) * | 2019-11-04 | 2020-03-31 | 广东丽臣奥威实业有限公司 | Preparation method of improved sodium dodecyl benzene sulfonate solution |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412056C (en) * | 2006-05-19 | 2008-08-20 | 上海世景国际贸易有限公司 | 3-amino-4-hydroxy benzenesulfonic acid, 3-amino-4-hydroxy-5-nitro benzenesulfonic acid and their salts synthesizing method |
-
2002
- 2002-07-15 CN CN02140719.3A patent/CN1193985C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604670A (en) * | 2012-02-10 | 2012-07-25 | 胜利油田中胜环保有限公司 | Method for preparing raw material of oil sulfonate for displacing oil in oilfield |
| CN105670590A (en) * | 2015-12-31 | 2016-06-15 | 中国石油天然气股份有限公司 | Ternary composite system and surfactant suitable for high-temperature hypersalinity oil reservoir and preparation method of ternary composite system and surfactant |
| CN105670590B (en) * | 2015-12-31 | 2019-04-09 | 中国石油天然气股份有限公司 | Ternary composite system and surfactant suitable for high-temperature hypersalinity oil reservoir and preparation method of ternary composite system and surfactant |
| CN107827784A (en) * | 2017-10-30 | 2018-03-23 | 苏州市浒墅关化工添加剂有限公司 | A kind of preparation method of sodium heavy alkyl benzene sulfonate |
| CN110938022A (en) * | 2019-11-04 | 2020-03-31 | 广东丽臣奥威实业有限公司 | Preparation method of improved sodium dodecyl benzene sulfonate solution |
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| Publication number | Publication date |
|---|---|
| CN1193985C (en) | 2005-03-23 |
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Effective date of registration: 20210304 Address after: 100007 Oil Mansion, 9 North Avenue, Dongcheng District, Beijing, Dongzhimen Patentee after: PetroChina Company Limited Patentee after: Daqing Oilfield Co.,Ltd. Address before: 163454 Jean Lake Road, Heilongjiang, Daqing Patentee before: Daqing Oilfield Co.,Ltd. |
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