CN117049985B - High-carbon sodium alkylbenzenesulfonate and preparation method and application thereof - Google Patents
High-carbon sodium alkylbenzenesulfonate and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000011734 sodium Substances 0.000 title claims abstract description 54
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 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 title claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 41
- 239000003921 oil Substances 0.000 claims abstract description 41
- 239000003085 diluting agent Substances 0.000 claims abstract description 28
- -1 alkyl sodium benzenesulfonate Chemical compound 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002562 thickening agent Substances 0.000 claims abstract description 22
- 239000013543 active substance Substances 0.000 claims abstract description 13
- 229940077388 benzenesulfonate Drugs 0.000 claims abstract description 7
- 239000012043 crude product Substances 0.000 claims description 26
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 15
- 238000007670 refining Methods 0.000 claims description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 229940077386 sodium benzenesulfonate Drugs 0.000 abstract description 3
- AQQPJNOXVZFTGE-UHFFFAOYSA-N 2-octadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O AQQPJNOXVZFTGE-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 description 8
- VOXUGSKPRRVTJG-UHFFFAOYSA-N 2-triacontylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O VOXUGSKPRRVTJG-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 7
- 239000011552 falling film Substances 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- WSVDSBZMYJJMSB-UHFFFAOYSA-N octadecylbenzene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1 WSVDSBZMYJJMSB-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- BSNANZJDRITJRO-UHFFFAOYSA-N 2-docosylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O BSNANZJDRITJRO-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KQLHMARFTGBJHY-UHFFFAOYSA-N 2-octacosylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KQLHMARFTGBJHY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- BCDYINATEKYEIG-UHFFFAOYSA-N docosyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 BCDYINATEKYEIG-UHFFFAOYSA-N 0.000 description 2
- MEYUFRQDILUMEC-UHFFFAOYSA-N docosylbenzene Chemical compound CCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1 MEYUFRQDILUMEC-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- DEQLTFPCJRGSHW-UHFFFAOYSA-N hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1 DEQLTFPCJRGSHW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- XRUUVYWRIFTORW-UHFFFAOYSA-N docosyl benzenesulfonate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 XRUUVYWRIFTORW-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- RNLHVNMGMAMAHJ-UHFFFAOYSA-N triacontylbenzene Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC1=CC=CC=C1 RNLHVNMGMAMAHJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a high-carbon sodium alkyl benzene sulfonate and a preparation method and application thereof. The high-carbon sodium alkyl benzene sulfonate comprises the following components in percentage by mass: 8-30% of high-carbon alkylbenzene, 3-10% of sulfur trioxide, 15-20% of 32% sodium hydroxide solution, 10-20% of diluent oil, 30-60% of thickening agent and 0.05-0.1% of pH regulator; wherein the higher alkylbenzene is selected from higher alkylbenzenes with 16-30 carbon atoms. The high-carbon alkyl sodium benzenesulfonate prepared by the invention has the advantages of simple raw material components, high purity and stable quality, the active substance content in the product is up to 60%, the water content is less than or equal to 5%, the appearance is reddish brown flowing liquid, the use environment is good, and the application of the high-carbon alkyl sodium benzenesulfonate in the field of three-production in oil fields is facilitated. The preparation method adopted by the invention is simple, is easy for industrialized mass production, has low cost and simple and convenient operation, is environment-friendly and green in the whole preparation process, and can obtain great economic benefit.
Description
Technical Field
The application relates to the technical field of sulfonate preparation, in particular to sodium high-carbon alkylbenzenesulfonate, and a preparation method and application thereof.
Background
At present, the method for three-production in the oil field mainly comprises the following steps: thermal flooding, mixed phase flooding, chemical flooding, microbial flooding and the like are becoming the mainstream of the oil field triple mining technology with continuous research and vigorous development of the oil field triple mining technology at home and abroad. Chemical flooding, as the name implies, is to add certain chemicals to the reservoir injection water to change the properties of the displacement fluid and the interface between the displacement fluid and the crude oil. In chemical flooding, the compound flooding is one of the most commercially viable methods at present, and the development of the surfactant mainly depends on the compound flooding is one of the bottleneck technologies which restrict the large-area popularization of the compound flooding.
In the following, the surfactant (hereinafter referred to as "surfactant") mainly used is sodium petroleum sulfonate, but the material has the defects of complex raw material composition, low content of main active substances (only 5-15%), low yield of finished products (about 50%), low interfacial activity, insignificant effect and the like when in use.
Therefore, the preparation of a surfactant with high activity and stable performance is an urgent problem to be solved.
Disclosure of Invention
In order to at least partially solve any one of the technical problems, the embodiment of the invention provides the high-carbon sodium alkylbenzenesulfonate surfactant with high active substance content, high yield and stable performance, and simultaneously provides a preparation method which has simple production process and can be used for industrial production.
In a first aspect, the invention provides a sodium higher alkylbenzenesulfonate, which comprises the following components in percentage by mass: 8-30% of high-carbon alkylbenzene, 3-10% of sulfur trioxide, 15-20% of 32% sodium hydroxide solution, 10-20% of diluent oil, 30-60% of thickening agent and 0.05-0.1% of pH regulator;
the higher alkylbenzene is selected from higher alkylbenzenes with 16-30 carbon atoms.
In any one of the embodiments, the diluent oil is selected from one or more of 150n,150sn, or PA 8.
In any one of the embodiments, the viscosity reducing agent is selected from the group consisting of heavy alkylbenzene sulfonic acid and/or sodium heavy alkylbenzene sulfonate.
In any one of the embodiments, the pH adjuster is selected from one or more of citric acid, monoethanolamine, or diethanolamine.
In any one of the specific embodiments, in the sodium high-carbon alkylbenzenesulfonate, the content of active substances is 40-60%, and the moisture content is less than or equal to 5%.
In a second aspect, the present application relates to a process for preparing the above-mentioned sodium higher alkylbenzenesulfonate, said process comprising the steps of:
s1, preparation of high-carbon alkylbenzene sulfonic acid crude product
Mixing high-carbon alkylbenzene and sulfur trioxide, and raising the temperature to obtain a high-carbon alkylbenzene sulfonic acid crude product;
s2, refining of higher alkylbenzenesulfonic acid
Removing impurities from the crude product of the high-carbon alkylbenzene sulfonic acid prepared in the step S1, aging, and adding water for refining to obtain the high-carbon alkylbenzene sulfonic acid;
S3, preparation of sodium higher alkylbenzenesulfonate
And (3) sequentially adding a thickening agent and diluent oil into the high-carbon alkylbenzene sulfonic acid obtained in the step (S2), stirring and mixing, adding alkali liquor, performing neutralization reaction, adding a pH regulator, regulating the pH value of the reaction liquid, and carrying out vacuum dehydration to obtain the high-carbon alkylbenzene sodium sulfonate.
In any one of the embodiments, the molar ratio of the higher alkylbenzene to the sulfur trioxide is 1: (0.90-1.10).
In any one of the specific embodiments, the water is added in an amount of 0.3 to 0.6% by mass of the crude higher alkylbenzene sulfonic acid product.
In a third aspect, the application of the sodium higher alkylbenzenesulfonate in three-production in oil fields is disclosed.
Compared with the prior art, the invention has the following advantages:
1. The existing raw materials of the petroleum sodium sulfonate mainly come from petroleum fractions, and the raw materials have complex composition; the prepared petroleum sodium sulfonate has low yield, insufficient purity, high viscosity and brown to reddish brown paste appearance, is poor in use environment and needs to be heated for use; the components of the composition comprise active substances, jelly, inorganic salt, unsulfonate, water and the like; meanwhile, the preparation process is a kettle type reactor, so that the application of the petroleum sodium sulfonate in the field of three-production of oil fields is greatly restricted. The high-carbon alkyl sodium benzenesulfonate prepared by the invention has the advantages of simple raw material components, high purity and stable quality, the active substance content in the product is up to 60%, the water content is not more than 5%, the product is a reddish brown flowing liquid, the use environment is good, and the application of the product in the field of three-production of oil fields is facilitated.
2. The preparation method adopted by the invention is simple, is easy for industrialized mass production, has low cost and simple and convenient operation, is environment-friendly and green in the whole preparation process, and can obtain great economic benefit.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims.
Detailed Description
The petroleum sodium sulfonate as the surfactant for compound flooding has the advantages of being capable of being synthesized by local materials, simple in process flow, mature, easy to operate, low in cost and good in interfacial tension performance. However, the petroleum sulfonate raw material composition is complex, so that the production process parameters are difficult to determine, the product performance is unstable due to the large amount of byproducts in the sulfonation process, and the purification process is complicated.
The inventor also finds that in practical application: among sodium petroleum sulfonates, there are also: the main active material content is low (only 5-15%), the finished product yield is low (about 50%), and the defects of low interfacial activity, insignificant effect and the like when in use are overcome. The above technical problems are not reported in the prior art.
The present invention has been made by the inventors in view of the fact that the prior art is inferior to the inventors' expectation, through further studies.
The invention provides high-carbon sodium alkyl benzene sulfonate, which comprises the following components in percentage by mass: 8-30% of high-carbon alkylbenzene, 3-10% of sulfur trioxide, 15-20% of 32% sodium hydroxide solution, 10-20% of diluent oil, 30-70% of thickening agent and 0.05-0.1% of pH regulator;
the higher alkylbenzene is selected from higher alkylbenzenes with 16-30 carbon atoms.
The surfactant product with high purity, stable quality, active substance content up to 60% and water content not more than 5% can be prepared by simple raw material composition, has the appearance of reddish brown flowing liquid, is environment-friendly, and is beneficial to large-scale application in the field of oilfield triple production.
The invention also designs and proposes a method for preparing the high-carbon sodium alkylbenzenesulfonate, which comprises the following steps:
s1, preparation of high-carbon alkylbenzene sulfonic acid crude product
Mixing high-carbon alkylbenzene and sulfur trioxide, and raising the temperature to obtain a high-carbon alkylbenzene sulfonic acid crude product;
s2, refining of higher alkylbenzenesulfonic acid
Removing impurities from the crude product of the high-carbon alkylbenzene sulfonic acid prepared in the step S1, aging, and adding water for refining to obtain the high-carbon alkylbenzene sulfonic acid;
S3, preparation of sodium higher alkylbenzenesulfonate
And (3) sequentially adding a thickening agent and diluent oil into the high-carbon alkylbenzene sulfonic acid obtained in the step (S2), stirring and mixing, adding alkali liquor, performing neutralization reaction, adding a pH regulator, regulating the pH value of the reaction liquid, and carrying out vacuum dehydration to obtain the high-carbon alkylbenzene sodium sulfonate.
The preparation method adopted by the invention is simple, easy for industrial mass production, low in cost and simple and convenient to operate, and the clean treatment of impurities, wastes and the like is also considered in the preparation process, so that the whole production process is environment-friendly, and great economic benefit can be obtained.
The application is described in further detail below with reference to specific examples, wherein the sources of materials are generally commercially available.
Example 1
The high-carbon sodium alkylbenzenesulfonate comprises the following components in percentage by mass: 8wt% of hexadecyl benzene, 3wt% of sulfur trioxide, 15wt% of 32% NaOH (aq), 10wt% of 150N diluent oil, 30wt% of heavy alkylbenzene sulfonic acid (thickening agent) and 0.05wt% of citric acid (pH regulator);
The preparation of the sodium hexadecyl benzene sulfonate in the embodiment comprises the following steps according to the formula amount:
preparation of S1, hexadecyl benzene sulfonic acid crude product
Mixing hexadecyl benzene and sulfur trioxide gas in a multitube falling film type sulfonation reactor, and controlling the temperature of the reactor to be 40 ℃ to obtain a hexadecyl benzene sulfonic acid crude product;
refining of S2, hexadecyl benzene sulfonic acid
Feeding the crude hexadecyl benzenesulfonic acid product prepared in the step S1 into a pretreatment tank, and removing impurities such as sulfur trioxide gas, waste acid and the like through rotary centrifugation; feeding the pretreated hexadecyl benzene sulfonic acid into an aging device, adding 0.3% pure water (relative to the mass of the pretreated hexadecyl benzene sulfonic acid) for aging and hydrolyzing for 4 hours to obtain hexadecyl benzene sulfonic acid;
Preparation of S3, sodium hexadecyl benzene sulfonate
Adding a thickening agent and diluent oil into the hexadecyl benzene sulfonic acid obtained in the step S2 in sequence, stirring and mixing, adding 32% NaOH (aq, sodium hydroxide solution) into the mixed solution, adding a pH regulator after 2 hours, regulating the pH value of the solution to 7, and carrying out vacuum dehydration to obtain sodium hexadecyl benzene sulfonate.
Example 2
The high-carbon sodium alkylbenzenesulfonate comprises the following components in percentage by mass: 15wt% of octadecylbenzene, 5wt% of sulfur trioxide, 15wt% of 32% NaOH (aq), 5wt% of 150N diluent oil and 5wt% of 150SN diluent oil, 40wt% of heavy alkylbenzene sulfonic acid (thickening agent) and 0.05wt% of diethanolamine (pH regulator);
The preparation of the sodium stearyl benzene sulfonate in the embodiment comprises the following steps according to the formula amount:
preparation of S1, octadecyl benzene sulfonic acid crude product
Mixing octadecyl benzene and sulfur trioxide gas in a multitube falling film sulfonation reactor, and controlling the temperature of the reactor to be 40 ℃ to obtain an octadecyl benzene sulfonic acid crude product;
Refining of S2, octadecyl benzene sulfonic acid
Feeding the octadecyl benzene sulfonic acid crude product prepared in the step S1 into a pretreatment tank, and removing impurities such as sulfur trioxide gas, waste acid and the like through rotary centrifugation; and (3) sending the pretreated octadecyl benzenesulfonic acid into an aging device, adding 0.35% pure water (relative to the mass of the pretreated octadecyl benzenesulfonic acid), aging and hydrolyzing for 4 hours, and obtaining the octadecyl benzenesulfonic acid.
Preparation of S3, sodium octadecyl benzene sulfonate
Sequentially adding a thickening agent and diluent oil into the octadecyl benzene sulfonic acid obtained in the step S2, stirring and mixing, then adding 32% NaOH (aq, sodium hydroxide solution) into the mixed solution, adding a pH regulator after 2 hours, regulating the pH value of the solution to 7, and carrying out vacuum dehydration to obtain sodium octadecyl benzene sulfonate;
example 3
The high-carbon sodium alkylbenzenesulfonate comprises the following components in percentage by mass: 20wt% of octadecyl benzene, 5wt% of sulfur trioxide, 18wt% of 32% NaOH (aq), 15wt% of PA8 diluent oil, 40wt% of sodium heavy alkylbenzenesulfonate (thickening agent), 0.05wt% of diethanolamine and 0.03wt% of citric acid (pH regulator);
The preparation of the sodium stearyl benzene sulfonate in the embodiment comprises the following steps according to the formula amount:
preparation of S1, octadecyl benzene sulfonic acid crude product
Mixing octadecyl benzene and sulfur trioxide gas in a multitube falling film sulfonation reactor, and controlling the temperature of the reactor to be 40 ℃ to obtain an octadecyl benzene sulfonic acid crude product;
Refining of S2, octadecyl benzene sulfonic acid
Feeding the octadecyl benzene sulfonic acid crude product prepared in the step S1 into a pretreatment tank, and removing impurities such as sulfur trioxide gas, waste acid and the like through rotary centrifugation; feeding the pretreated octadecyl benzene sulfonic acid into an aging device, adding 0.4% pure water (relative to the mass of the pretreated octadecyl benzene sulfonic acid), aging and hydrolyzing for 4 hours to obtain the octadecyl benzene sulfonic acid;
Preparation of S3, sodium octadecyl benzene sulfonate
Sequentially adding a thickening agent and diluent oil into the octadecyl benzene sulfonic acid obtained in the step S2, stirring and mixing, then adding 32% NaOH (aq, sodium hydroxide solution) into the mixed solution, adding a pH regulator after 2 hours, regulating the pH value of the solution to 7, and carrying out vacuum dehydration to obtain sodium octadecyl benzene sulfonate.
Example 4
The high-carbon sodium alkylbenzenesulfonate comprises the following components in percentage by mass: 24wt% of octadecylbenzene, 8wt% of sulfur trioxide, 18wt% of 32% NaOH (aq), 2wt% of 150N diluent oil, 3wt% of 150SN diluent oil, 15wt% of PA8 diluent oil, 50wt% of heavy alkylbenzenesulfonic acid (thickening agent), 0.02 wt% of monoethanolamine, 0.03wt% of diethanolamine, and 0.05wt% of citric acid (pH regulator);
The preparation of the sodium stearyl benzene sulfonate in the embodiment comprises the following steps according to the formula amount:
preparation of S1, octadecyl benzene sulfonic acid crude product
Mixing octadecyl benzene and sulfur trioxide gas in a multitube falling film sulfonation reactor, and controlling the temperature of the reactor to be 40 ℃ to obtain an octadecyl benzene sulfonic acid crude product;
Refining of S2, octadecyl benzene sulfonic acid
Feeding the octadecyl benzene sulfonic acid crude product prepared in the step S1 into a pretreatment tank, and removing impurities such as sulfur trioxide gas, waste acid and the like through rotary centrifugation; and (3) sending the pretreated octadecyl benzenesulfonic acid into an aging device, adding 0.4% pure water (relative to the mass of the pretreated octadecyl benzenesulfonic acid), aging and hydrolyzing for 4 hours, and obtaining the octadecyl benzenesulfonic acid.
Preparation of S3, sodium octadecyl benzene sulfonate
Sequentially adding a thickening agent and diluent oil into the octadecyl benzene sulfonic acid obtained in the step S2, stirring and mixing, then adding 32% NaOH (aq, sodium hydroxide solution) into the mixed solution, adding a pH regulator after 2 hours, regulating the pH value of the solution to 7, and carrying out vacuum dehydration to obtain sodium octadecyl benzene sulfonate;
Example 5
The high-carbon sodium alkylbenzenesulfonate comprises the following components in percentage by mass: 24wt% of behenyl benzene, 6wt% of sulfur trioxide, 18wt% of 32% NaOH (aq), 5wt% of 150N diluent oil and 5wt% of 150SN diluent oil, 40wt% of heavy alkylbenzene sulfonic acid and 20wt% of sodium heavy alkylbenzene sulfonate (thickening agent), and 0.05wt% of diethanolamine (pH regulator);
The preparation of the sodium behenyl benzenesulfonate in the embodiment comprises the following steps according to the formula amount:
Preparation of crude S1, sedocosyl benzenesulfonic acid product
Mixing the behenyl benzene and sulfur trioxide gas in a multitube falling film sulfonation reactor, and controlling the temperature of the reactor to be 40 ℃ to obtain a behenyl benzenesulfonic acid crude product;
Refining of S2, behenyl benzenesulfonic acid
Delivering the crude product of the behenyl benzenesulfonic acid prepared in the step S1 into a pretreatment tank, and removing impurities such as sulfur trioxide gas, waste acid and the like through rotary centrifugation; delivering the pretreated docosane benzenesulfonic acid into an aging device, adding 0.48% pure water (relative to the mass of the pretreated docosane benzenesulfonic acid), aging and hydrolyzing for 4 hours to obtain the docosane benzenesulfonic acid;
preparation of sodium S3, behenyl benzenesulfonate
And (3) sequentially adding a thickening agent and diluent oil into the behenyl benzenesulfonic acid obtained in the step (S2), stirring and mixing, adding 32% NaOH (aq, sodium hydroxide solution) into the mixed solution, adding a pH regulator after 2 hours, regulating the pH value of the solution to 7, and carrying out vacuum dehydration to obtain the sodium behenyl benzenesulfonate.
Example 6
The high-carbon sodium alkylbenzenesulfonate comprises the following components in percentage by mass: 30wt% of octacosanyl benzene, 5wt% of sulfur trioxide, 20wt% of 32% NaOH (aq), 5wt% of 150N diluent oil and 5wt% of 150SN diluent oil, 30wt% of heavy alkylbenzene sulfonic acid and 20wt% of sodium heavy alkylbenzene sulfonate (thickening agent), and 0.1wt% of diethanolamine (pH regulator);
the preparation of the sodium octacosyl benzene sulfonate in the embodiment comprises the following steps according to the formula amount:
preparation of crude S1, octacosyl benzenesulfonic acid
Mixing octacosane benzene and sulfur trioxide gas in a multitube falling film sulfonation reactor, and controlling the temperature of the reactor to be 40 ℃ to obtain octacosane benzenesulfonic acid crude product;
Refining of S2, octacosyl benzene sulfonic acid
Conveying the crude octacosane benzenesulfonic acid product prepared in the step S1 into a pretreatment tank, and removing impurities such as sulfur trioxide gas, waste acid and the like through rotary centrifugation; feeding the pretreated octacosane benzenesulfonic acid into an aging device, adding 0.52% pure water (relative to the mass of the pretreated octacosane benzenesulfonic acid), aging and hydrolyzing for 4 hours to obtain octacosane benzenesulfonic acid;
preparation of S3, octacosyl sodium benzenesulfonate
And (3) sequentially adding a thickening agent and diluent oil into the octacosane benzenesulfonic acid obtained in the step (S2), stirring and mixing, adding 32% NaOH (aq, sodium hydroxide solution) into the mixed solution, adding a pH regulator after 2 hours, regulating the pH value of the solution to 7, and carrying out vacuum dehydration to obtain octacosane benzenesulfonic acid sodium.
Example 7
The high-carbon sodium alkylbenzenesulfonate comprises the following components in percentage by mass: 30wt% of triacontanebenzene, 5wt% of sulfur trioxide, 18wt% of 32% NaOH (aq), 15wt% of PA8 diluent oil, 40wt% of sodium heavy alkylbenzenesulfonate (thickening agent), 0.05wt% of diethanolamine and 0.03wt% of citric acid (pH regulator);
The preparation of the sodium triacontyl benzene sulfonate comprises the following steps according to the formula amount:
s1, preparation of triacontyl benzene sulfonic acid crude product
Mixing triacontyl benzene and sulfur trioxide gas in a multitube falling film sulfonation reactor, and controlling the temperature of the reactor to be 40 ℃ to obtain a triacontyl benzene sulfonic acid crude product;
S2, refining of triacontyl benzene sulfonic acid
Feeding the crude product of the triacontyl benzene sulfonic acid prepared in the step S1 into a pretreatment tank, and removing impurities such as sulfur trioxide gas, waste acid and the like through rotary centrifugation; feeding the pretreated triacontyl benzene sulfonic acid into an aging device, adding 0.6% pure water (relative to the mass of the pretreated triacontyl benzene sulfonic acid) for aging and hydrolyzing for 4 hours to obtain triacontyl benzene sulfonic acid;
Preparation of S3, sodium triacontyl benzene sulfonate
And (3) sequentially adding a thickening agent and diluent oil into the triacontyl benzene sulfonic acid obtained in the step (S2), stirring and mixing, then adding 32% NaOH (aq, sodium hydroxide solution) into the mixed solution, adding a pH regulator after 2 hours, regulating the pH value of the solution to 7, and carrying out vacuum dehydration to obtain the sodium triacontyl benzene sulfonate.
Comparative example 1
The difference from example 1 is that: sodium dodecyl benzene sulfonate is selected to replace sodium hexadecyl benzene sulfonate.
The properties of examples 1 to 7 and comparative example 1 were measured to obtain the data shown in Table 1.
Table 1 results of the tests of examples 1 to 7
| Purity of high-carbon alkylbenzenesulfonic acid after refining | Active substance content | Moisture content | |
| Example 1 | 82％ | 44.25％ | 4.8％ |
| Example 2 | 84％ | 45.92％ | 3.2％ |
| Example 3 | 88％ | 47.74％ | 2.8％ |
| Example 4 | 85％ | 46.49％ | 3.0％ |
| Example 5 | 83％ | 46.15％ | 3.2％ |
| Example 6 | 83％ | 48.76％ | 2.4％ |
| Example 7 | 82％ | 48.03％ | 2.3％ |
| Comparative example 1 | 85％ | 33.20％ | 10.8％ |
From the test results of Table 1, in combination with examples 1 to 7 and comparative example 1, we can see: the high-carbon alkylbenzene sodium sulfonate prepared by the method has the active material content of not less than 40% and the moisture content of not more than 5% when the high-carbon alkylbenzene with the carbon number of 16-30 is selected as the raw materials.
Furthermore, in connection with examples 1 to 7, it can be seen that when using higher alkylbenzenes having 18 to 30 carbon atoms, the purity of the higher alkylbenzene sulfonic acid, the active material content and the water content in the sodium higher alkylbenzene sulfonate are all at a preferable level.
In order to further increase the content of active substances in the sodium higher alkylbenzenesulfonate and to further decrease the moisture content, the following experiment was designed by adjusting the ratio between the partial materials by taking example 3 as an example.
The inventors guess through experience: in the preparation of sodium higher alkylbenzene sulfonate, the ratio of higher alkylbenzene to sulfur trioxide had a certain effect on the active material content and moisture content, and examples 8 to 12 were made. To verify that the guesses were correct, the amounts of higher alkylbenzenes and sulfur trioxide added in examples 8 to 12 are shown in Table 2, and the results of the measurements are recorded therein.
Table 2 data parameters and test results in examples 8 to 12
From examples 3 and 8-12 and their property measurements we can find that: in the composition range of the raw materials, the high-carbon sodium alkylbenzenesulfonate prepared by the application has higher active substance content and lower moisture content. Furthermore, we have found that the active substance content and the moisture content in sodium higher alkylbenzene sulfonate are not in a simple linear relationship with the molar ratio of higher alkylbenzene to sulfur trioxide, and can be obtained from the table, in particular: when the molar ratio of higher alkylbenzene to sulfur trioxide is controlled at position 1: (0.9-1.1), the active substance content in the high-carbon sodium alkylbenzenesulfonate prepared by the application is up to 60%, and the water content is lower than 1%.
The high-carbon sodium alkyl benzene sulfonate (HAS) prepared in example 11 with different concentrations (0.1%, 0.2% and 0.4%) is taken as a surfactant, and injected into the formation water of the Bohai sea oil field (the composition of the experimental water is shown in the following table 3) for interfacial tension experiments, and the results are shown in table 4. The test instrument used was a Sigma 703D interfacial tensiometer, the test temperature was controlled at t=35 ℃, the test time 300s. The following are application examples 1 to 6 of the present application.
Table 3 composition of experimental water
Table 4 interfacial tension test data
The application adopts petroleum sodium sulfonate as a surfactant in the prior art as an application comparative example, and under the same condition, an interfacial tension test is carried out to find that: after the treatment with sodium petroleum sulfonate, the water interfacial tension generally decreased to 1×10 -2 mN/m, and compared with the treatment effect of the sodium higher alkylbenzenesulfonate we used, we can see from table 4: even if the sodium higher alkylbenzenesulfonate is used in an amount of 0.1%, the water interfacial tension can be reduced to 1X 10 -3 mN/m by one order of magnitude. Therefore, the high-carbon sodium alkyl benzene sulfonate prepared by the application has lower interfacial activity and low oil displacement effect when in use.
The oil displacement test was performed on the above application examples 1 to 6, and the oil displacement test results shown in table 5 were obtained.
Table 5 results of oil displacement experiments
In combination with the test results of application examples 1 to 6 and the application comparative example, we can find that: on the basis of water flooding, the high-carbon sodium alkyl benzene sulfonate compound oil displacement system can further improve the crude oil recovery ratio by about 30-35%, and the total crude oil recovery ratio reaches about 80%.
The foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, but various modifications or applications according to the foregoing embodiment are all within the scope of the present invention.
Although specific embodiments of the invention have been described in detail, those skilled in the art will appreciate. Numerous modifications and substitutions of details are possible in light of all the teachings disclosed, and such modifications are contemplated as falling within the scope of the present invention. The full scope of the invention is given by the appended claims and any equivalents thereof.
Claims (2)
1. A method for preparing a high-carbon sodium alkylbenzenesulfonate solution, which is characterized by comprising the following steps:
s1, preparation of high-carbon alkylbenzene sulfonic acid crude product
Mixing high-carbon alkylbenzene and sulfur trioxide, and raising the temperature to obtain a high-carbon alkylbenzene sulfonic acid crude product;
s2, refining of higher alkylbenzenesulfonic acid
Removing impurities from the crude product of the high-carbon alkylbenzene sulfonic acid prepared in the step S1, aging, and adding water for refining to obtain the high-carbon alkylbenzene sulfonic acid;
S3, preparation of sodium higher alkylbenzenesulfonate
Sequentially adding a thickening agent and diluent oil into the high-carbon alkylbenzene sulfonic acid obtained in the step S2, stirring and mixing, adding 32% sodium hydroxide solution, carrying out neutralization reaction, adding a pH regulator, regulating the pH value of the reaction solution, and carrying out vacuum dehydration to obtain high-carbon alkylbenzene sodium sulfonate solution;
The weight percentage of each component is as follows: 8-30% of high-carbon alkylbenzene, 3-10% of sulfur trioxide, 15-20% of 32% sodium hydroxide solution, 10-20% of diluent oil, 30-60% of thickening agent and 0.05-0.1% of pH regulator;
the high-carbon alkylbenzene is selected from high-carbon alkylbenzenes with the carbon number of 16-30;
the thickening agent is selected from heavy alkylbenzene sulfonic acid and/or sodium heavy alkylbenzene sulfonate;
in S1, the molar ratio of the higher alkylbenzene to the sulfur trioxide is 1: (0.90-1.10);
The diluent oil is selected from one or more of 150N,150SN or PA 8;
the pH regulator is one or more selected from citric acid, monoethanolamine or diethanolamine;
In the high-carbon sodium alkyl benzene sulfonate solution, the content of active substances is 40-60%, and the moisture content is less than or equal to 5%.
2. The preparation method according to claim 1, wherein in S2, the water is added in an amount of 0.3 to 0.6% based on the total mass of the crude higher alkylbenzene sulfonic acid product.
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