CN114539102B - Process for preparing petroleum sulfonate - Google Patents
Process for preparing petroleum sulfonate Download PDFInfo
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- CN114539102B CN114539102B CN202011349129.5A CN202011349129A CN114539102B CN 114539102 B CN114539102 B CN 114539102B CN 202011349129 A CN202011349129 A CN 202011349129A CN 114539102 B CN114539102 B CN 114539102B
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- petroleum sulfonate
- organic solvent
- sulfonating agent
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 53
- 239000003208 petroleum Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 27
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 44
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical group CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000011552 falling film Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 claims description 3
- 238000004939 coking Methods 0.000 abstract description 14
- 239000004094 surface-active agent Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000002585 base Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 42
- 239000002253 acid Substances 0.000 description 18
- 239000013543 active substance Substances 0.000 description 18
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229940055577 oleyl alcohol Drugs 0.000 description 9
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 alkylbenzene sulfonate Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C303/08—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 halogenosulfonic 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
- C07C303/32—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a petroleum sulfonate preparation method, which comprises the following steps of S1, mixing raw oil with aromatic hydrocarbon content more than 18% with an alcohol organic solvent to form a mixture to be reacted; wherein the mass ratio of the raw oil to the alcohol organic solvent is 100:0.5-6; step S2, the mixture to be reacted fully reacts with a sulfonating agent, wherein the mol ratio of the sulfonating agent to raw oil is 1:1.05-1.3; and step S3, the sulfonation product obtained in the step S2 is subjected to neutralization reaction with an alkali solution to obtain petroleum sulfonate. The invention solves the problems of easy coking, short sulfonation period and the like in the production process of the high-viscosity oil, widens the raw material adaptability, and obtains one or more weak base system surfactants with wide raw material sources, low production cost and stable interfacial tension.
Description
Technical Field
The invention relates to the field of petrochemical assistants, in particular to a preparation method of a petroleum sulfonate surfactant.
Background
Petroleum sulfonate is an anionic surfactant synthesized from petroleum fractions. According to the national energy demand, the main surface active agents for the chemical flooding lead test, the mine field test and the industrialized popularization test of the current oil field mainly take petroleum sulfonate and alkylbenzene sulfonate for oil displacement as main bodies, and the demand of the two surface active agents is very large. The petroleum sulfonate has the problems of easy sulfonation coking, short sulfonation period, poor quality stability, poor salt resistance and temperature resistance, larger adsorption heat loss, lower reaction yield and the like, wherein the short sulfonation period is caused by reactor blockage due to coking, periodic cleaning is required, and the problems bring difficulty to scientific research and large-scale production.
Through many years of research and exploration, some petroleum sulfonate preparation methods with improved significance are developed, but the prior art still has partial defects. For example, chinese invention CN108485625a relates to an anionic surfactant thickened oil viscosity-reducing oil-displacing agent and a preparation method thereof, wherein long-chain polyether amine and methyl acrylate are subjected to addition reaction in a solvent according to a certain molar ratio. However, the method is viscosity reduction during oil extraction, and is not viscosity reduction during preparation, and still has the coking problem. Chinese patent No. 106243002A relates to a petroleum sulfonate oil displacement agent and a preparation method thereof, wherein ketone benzene dewaxed oil or furfural extract oil is subjected to sulfonation reaction with sulfur trioxide, and petroleum sulfonate is obtained after neutralization. Although the method improves the reaction yield, no other solvent is added in the reaction process, the reaction is easy to coke, and the cleaning period of the reactor is shorter. Chinese patent No. 104403652 discloses a preparation method of petroleum sulfonate surfactant for oil displacement. The preparation method adopts two-wire reduction, three-wire reduction and four-wire reduction vacuum distillate oil as a raw material, and petroleum sulfonate surfactant is obtained through sulfonation, aging, neutralization and other steps. However, in order to solve the coking problem caused by high viscosity of the raw materials, a large amount of solvent oil is added as a diluent in the preparation method. Although the method partially solves the coking problem, a large amount of solvent oil in the reaction process needs to be separated and recovered by using an organic solvent after sulfonation, so that the problems of complex process and environmental protection are caused.
Therefore, a method is needed to be found to solve the problems of coking and excessive acid sludge output and reactor blockage in the petroleum sulfonate preparation process without introducing a large amount of diluent.
Disclosure of Invention
The main purpose of the invention is to provide a preparation method of petroleum sulfonate, which solves the problems of coking and excessive acid sludge output and reactor blockage in the petroleum sulfonate preparation process by selecting and controlling the aromatic hydrocarbon content of raw oil and adding a small amount of alcohol organic solvent into the raw oil.
In the specific embodiment of the invention, the provided petroleum sulfonate preparation method comprises the following steps of S1, mixing raw oil with aromatic hydrocarbon content more than 18% with an alcohol organic solvent to form a mixture to be reacted; wherein the mass ratio of the raw oil to the alcohol organic solvent is 100:0.5-6; step S2, the mixture to be reacted fully reacts with a sulfonating agent, wherein the mol ratio of the sulfonating agent to raw oil is 1.05-1.3:1; and step S3, the sulfonation product obtained in the step S2 is subjected to neutralization reaction with an alkali solution to obtain petroleum sulfonate.
Further, the raw oil is distillate oil or extracted oil, and the aromatic hydrocarbon content of the raw oil is more than 40%.
Further, the alcohol organic solvent is one or more selected from isopropanol, n-butanol and dodecanol.
Further, the sulfonating agent is chlorosulfonic acid or sulfur trioxide.
In the specific embodiment provided by the invention, the mass ratio of the raw oil to the alcohol organic solvent is 100:3-4.
Further, the alkaline solution used in step S3 is sodium hydroxide solution.
In the specific embodiment provided by the invention, the reaction device adopted by the preparation method provided by the invention is a single-tube or multi-tube falling film reactor.
In a specific embodiment provided by the invention, the preparation method provided by the invention comprises the following steps: step S1, raw oil and an alcohol organic solvent are mixed uniformly in a container according to a proportion to form a mixture to be reacted; s2, diluting the sulfonating agent to a certain concentration by using the dried air, and then passing through a sulfonation reaction device; preheating the mixture to be reacted to the reaction temperature, and then pumping the mixture to the top of the sulfonation reaction device by a metering pump, and enabling the mixture to flow downwards in parallel with the air flow of the sulfonating agent, and uniformly forming a film along the inner wall of the sulfonation reaction device for full reaction; and S3, the sulfonated product and the metered alkali solution enter a neutralization reactor to carry out full neutralization reaction, and petroleum sulfonate is obtained.
Further, the reaction temperature in the step S2 is 40-70 ℃.
Further, the neutralization reaction temperature in the step S3 is 55-75 ℃.
According to the technical scheme provided by the invention, the petroleum sulfonate raw material is optimized, the minimum aromatic hydrocarbon content in the raw oil is determined, the petroleum sulfonate sulfonation process is optimized, the problem of easy coking in the high-viscosity oil production process is solved, the reactor blockage caused by coking is avoided, the problem of short sulfonation period caused by reactor blockage caused by coking is overcome, the raw material adaptability is widened, and one or more weak base system surfactants with wide raw material sources, low production cost and stable interfacial tension are obtained, which is also a key technology for popularizing and applying petroleum sulfonate.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
In order to further describe the objects, effects, and the technical means employed in the present invention in detail, the following description is made with reference to the specific embodiments.
As described in the background art, the existing petroleum sulfonate preparation method has the problems of easy sulfonation coking, short sulfonation period, poor quality stability, poor salt resistance and temperature resistance, large adsorption heat loss, low reaction yield and the like. The method comprises the steps of S1, mixing raw oil with aromatic hydrocarbon content more than 18% with an alcohol organic solvent to form a mixture to be reacted; wherein the mass ratio of the raw oil to the alcohol organic solvent is 100:0.5-6; step S2, the mixture to be reacted fully reacts with a sulfonating agent, wherein the mol ratio of the sulfonating agent to raw oil is 1.05-1.3:1; and step S3, the sulfonation product obtained in the step S2 is subjected to neutralization reaction with an alkali solution to obtain petroleum sulfonate.
According to the petroleum sulfonate preparation method provided by the invention, firstly, the minimum aromatic hydrocarbon content in the raw oil is optimized, and secondly, a small amount of alcohol organic solvent is added into the raw oil, so that the viscosity of the raw oil is reduced, and the coking problem in the sulfonation process is avoided. In addition, the alcohol organic solvent has the functions of viscosity reduction, solubilization and interfacial activity increase, and can be sulfonated in the sulfonation reaction, even if the alcohol organic solvent which is not sulfonated exists, the alcohol organic solvent can be dissolved in the product without recovery because the alcohol organic solvent occupies a small amount in the whole raw oil, so that the environmental protection problem caused by the recovery of a large amount of organic solvent is avoided.
Preferably, the raw oil is distillate oil or extract oil, and the aromatic hydrocarbon content of the raw oil is more than 40%, wherein the distillate oil is two-line, three-line and four-line reduced pressure distillate oil of a refinery, and the extract oil is oil obtained by removing solvent from extract liquid of petroleum fraction solvent refining.
In the specific embodiment provided by the invention, the alcohol organic solvent is one or more selected from isopropanol, n-butanol and dodecanol, and the sulfonating agent is chlorosulfonic acid and sulfur trioxide.
Preferably, in the specific embodiment provided by the invention, the mass ratio of the raw oil to the alcohol organic solvent is 100:3-4.
Further, in the specific embodiment provided by the present invention, the alkaline solution used in step S3 is a sodium hydroxide solution and/or a potassium hydroxide solution.
Preferably, the reaction device adopted by the preparation method provided by the invention is a single-tube or multi-tube falling film reactor.
In a specific embodiment provided by the invention, the preparation method comprises the following steps: step S1, raw oil and an alcohol organic solvent are mixed uniformly in a container according to a proportion to form a mixture to be reacted; s2, diluting the sulfonating agent to a certain concentration by using the dried air, and then passing through a sulfonation reaction device; the mixture to be reacted is preheated to the reaction temperature through a sleeve and then is pumped to the top of a sulfonation reaction device by a metering pump, and flows downwards in parallel with the air flow of the sulfonating agent, and is uniformly formed into a film along the inner wall of the reaction device to fully react; and S3, the sulfonated product and the metered alkali solution enter a neutralization reactor to carry out full neutralization reaction, and petroleum sulfonate is obtained. Preferably, the petroleum sulfonate product can be further purified using ethanol to yield high purity petroleum sulfonate. In addition, it is preferable that the sulfonation reaction temperature of step S2 is 40 to 70 ℃, more preferably 40 ℃, and the neutralization reaction temperature of step S3 is 55 to 70 ℃, more preferably 55 ℃.
Reaction device
The reaction device adopted by the invention is a single-tube or multi-tube falling film reactor. The length of the glass tube of the single tube is 1 meter, the length of each tube of the multi-tube falling film reactor is 3 tubes, and the length of each tube is 6 meters.
Interfacial tension testing method
The interfacial tension tester adopted by the invention is a Model TX-500C spin-drop interfacial tension tester, and the surfactant is prepared into the use concentration of 0.05-0.3% (wt) by using oilfield block simulated water, and the interfacial tension is a stable equilibrium value for testing for 2 hours.
Comparative example 1
100 g of distillate (aromatic hydrocarbon content 10.5% by weight) having an acid-hydrocarbon ratio (mol) of 1.1:1, the oil-alcohol ratio (wt) is 100:2, the reaction temperature is 45 ℃, the neutralization temperature is 60 ℃, the neutralized product is severely layered, and a uniform product cannot be obtained for active substance analysis and interfacial tension test. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, with the test results: the concentration of the active agent is 0.05 to 0.3 weight percent, the concentration of the alkali is 0.4 to 1.2 weight percent, and the minimum interfacial tension can reach 9.99 multiplied by 10 -2 mN/m-9.99×10 - 1 mN/m。
Comparative example 2
100 g of distillate (aromatic hydrocarbon content 30% by weight), based on an acid-hydrocarbon ratio (mol) of 1.1:1, the reaction is carried out at the reaction temperature of 45 ℃ and the neutralization temperature of 60 ℃, the neutralized product is severely layered, acid sludge is rapidly agglomerated at the bottom of the reactor in the reaction process, the reaction pressure is rapidly increased, the experiment can only be stopped for preventing danger, and the final reaction yield is 70%.
Example 1
100 g of distillate (aromatic hydrocarbon content 18% by weight), based on an acid to hydrocarbon ratio (mol) of 1.05:1, acid is chlorosulfonic acid, the ratio (wt) of oleyl alcohol to alcohol is 100:0.5, alcohol is isopropanol, the reaction temperature is 40 ℃, the neutralization temperature is 55 ℃, the petroleum sulfonate active matter in the reaction product is 18.11wt%, and the reaction yield is 86wt%. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, and the test results showed that: the minimum interfacial tension can reach 1.53 multiplied by 10 -3 mN/m。
Example 2
The feed was the same as in example 1, with an acid hydrocarbon (mol) ratio of 1.2:1, the acid is chlorosulfonic acid, and the oleyl alcohol (wt) ratio is 100:3, the alcohol is isopropanol, the reaction temperature is 50 ℃, the neutralization temperature is 60 ℃, the petroleum sulfonate active substance in the reaction product is 20.08 and wt%, and the reaction yield is 84.5wt%. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, and the test results showed that: the minimum interfacial tension can reach 3.88 multiplied by 10 -3 mN/m。
Example 3
100 g of distillate (aromatic hydrocarbon content 25.2% by weight) having an acid-hydrocarbon ratio (mol) of 1.1:1, acid is chlorosulfonic acid, the ratio (wt) of oleyl alcohol is 100:3, alcohol is isopropanol, the reaction temperature is 45 ℃, the neutralization temperature is 60 ℃, the petroleum sulfonate active matter in the reaction product is 24.5wt%, and the reaction yield is 85.6wt%. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, and the test results showed that: interfacial tension can reach 1.74×10 at minimum -3 mN/m。
Example 4
100 g of distillate (aromatic hydrocarbon content 25.2% by weight) having an acid-hydrocarbon ratio (mol) of 1.1:1, acid is chlorosulfonic acid, oilThe alcohol ratio (wt) is 100:4, the alcohol is isopropanol, the reaction temperature is 45 ℃, the neutralization temperature is 60 ℃, the petroleum sulfonate active substance in the reaction product is 23.0 and wt%, and the reaction yield is 87.3wt%. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, and the test results showed that: the minimum interfacial tension can reach 9.99 multiplied by 10 -4 mN/m。
Example 5
100 g (distillate + extract) (aromatic content 43.56 wt%) in terms of acid to hydrocarbon ratio (mol) 1.2:1, acid is chlorosulfonic acid, the ratio (wt) of oleyl alcohol is 100:3, alcohol is isopropanol, the reaction temperature is 55 ℃, the neutralization temperature is 65 ℃, the petroleum sulfonate active matter in the reaction product is 33.4 and wt%, and the reaction yield is 82.45wt%. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, and the test results showed that: the minimum interfacial tension can reach 2.49 multiplied by 10 -3 mN/m。
Example 6
100 g (distillate + extract) (aromatic content 43.56 wt%) in terms of acid to hydrocarbon ratio (mol) 1.3:1, acid is chlorosulfonic acid, the ratio (wt) of oleyl alcohol is 100:3, alcohol is isopropanol, the reaction temperature is 55 ℃, the neutralization temperature is 65 ℃, the petroleum sulfonate active matter in the reaction product is 32.16 wt%, and the reaction yield is 84.19wt%. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, and the test results showed that: the minimum interfacial tension can reach 5.30 multiplied by 10 -3 mN/m。
Example 7
100 g (distillate + extract) (aromatic content 40.1 wt%) in terms of acid to hydrocarbon ratio (mol) 1.2:1, acid is chlorosulfonic acid, the ratio (wt) of oleyl alcohol is 100:4, alcohol is isopropanol, the reaction temperature is 50 ℃, the neutralization temperature is 75 ℃, the petroleum sulfonate active matter in the reaction product is 34.1 wt%, and the reaction is carried outThe yield thereof was found to be 86.38% by weight. The interfacial tension of sulfonate was tested, in which the active agent concentration (wt%) test points were 0.05, 0.1, 0.2, 0.3, and the alkali concentration (wt%) test points were 0.4, 0.6, 0.8, 1.0, 1.2, and the test results showed that: the minimum interfacial tension can reach 5.60 multiplied by 10 -3 mN/m。
Example 8
With continuous feed, the feedstock was distillate oil (aromatic content 45.6 wt.%) at an acid to hydrocarbon ratio (mol) of 1.3:1, the oleyl alcohol ratio (wt) is 100:3, the reaction temperature is 60 ℃, the neutralization temperature is 75 ℃, the petroleum sulfonate active substance in the reaction product is 39.4 wt%, and the reaction yield is 97.2wt%. After 1-2 hours of intermediate control sampling, the sealed tank sampling analysis is carried out, and the interfacial tension of sulfonate is tested, wherein in the test, the active agent concentration (wt%) test points are 0.05, 0.1, 0.2 and 0.3, and the alkali concentration (wt%) test points are 0.4, 0.6, 0.8, 1.0 and 1.2, and the test result shows that: the minimum interfacial tension can reach 1.98 multiplied by 10 -3 mN/m。
Example 9
With continuous feed, the feed was distillate + extract (aromatic content 43.56 wt%) at an acid to hydrocarbon ratio (mol) of 1.3:1, the oleyl alcohol ratio (wt) is 100:3, the reaction temperature is 70 ℃, the neutralization temperature is 75 ℃, the petroleum sulfonate active substance in the reaction product is 36.6 wt%, and the reaction yield is 98.1wt%. After 1-2 hours of intermediate control sampling, the sealed tank sampling analysis is carried out, and the interfacial tension of sulfonate is tested, wherein in the test, the active agent concentration (wt%) test points are 0.05, 0.1, 0.2 and 0.3, and the alkali concentration (wt%) test points are 0.4, 0.6, 0.8, 1.0 and 1.2, and the test result shows that: the minimum interfacial tension can reach 6.87 multiplied by 10 -4 mN/m。
Example 10
With continuous feed, the feed was distillate + extract (aromatic content 43.56 wt%) at an acid to hydrocarbon ratio (mol) of 1.3:1, the oleyl alcohol ratio (wt) is 100:6, the reaction temperature is 70 ℃, the neutralization temperature is 75 ℃, the petroleum sulfonate active substance in the reaction product is 40.1 and wt%, and the reaction yield is 97.9wt%. Sampling and analyzing the sealed tank after 1-2 hours of intermediate control sampling, and testing the interfacial tension of sulfonateThe concentration (wt%) test points of the active agent are 0.05, 0.1, 0.2 and 0.3, the concentration (wt%) test points of the alkali are 0.4, 0.6, 0.8, 1.0 and 1.2, and the test results show that: the minimum interfacial tension can reach 1.98 multiplied by 10 -3 mN/m。
As can be seen from the above examples, the above petroleum sulfonate preparation method of the present invention can achieve higher reaction yield (82.45 wt% -98.1 wt%) and lower interfacial tension, and can reach 9.99X10 at the lowest -4 mN/m. Therefore, the petroleum sulfonate preparation method can avoid reactor blockage caused by coking, so that the obtained product has high yield and excellent performance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for preparing petroleum sulfonate, said method comprising:
step S1, mixing raw oil with aromatic hydrocarbon content more than or equal to 18% and less than or equal to 45.6% with an alcohol organic solvent to form a mixture to be reacted; wherein the mass ratio of the raw oil to the alcohol organic solvent is 100:3-4;
step S2, the mixture to be reacted fully reacts with a sulfonating agent, wherein the molar ratio of the sulfonating agent to raw oil is 1.05-1.3:1;
step S3, the sulfonated product obtained in the step S2 is subjected to neutralization reaction with an alkali solution to obtain the petroleum sulfonate;
the raw oil is distillate oil and/or extracted oil, and the alcohol organic solvent is isopropanol;
the sulfonating agent is chlorosulfonic acid.
2. The method according to claim 1, wherein the alkaline solution used in the step S3 is sodium hydroxide solution.
3. The method according to claim 1, wherein the sulfonation reaction apparatus used in the method is a single-tube or multi-tube falling film reactor.
4. A method of preparation according to claim 3, characterized in that the method of preparation comprises:
step S1, the raw oil and the alcohol organic solvent are fully and uniformly stirred in a container according to the proportion to form the mixture to be reacted;
s2, diluting the sulfonating agent to a certain concentration by using the dried air, and then introducing the diluted sulfonating agent into the sulfonation reaction device; the mixture to be reacted is preheated to the reaction temperature and then is pumped to the top of the sulfonation reaction device by a metering pump, and flows downwards in parallel with the air flow formed by the sulfonating agent, and is uniformly formed into a film along the inner wall of the sulfonation reaction device to fully react;
and S3, the sulfonated product and the metered alkali solution enter a neutralization reactor to carry out neutralization reaction, and the petroleum sulfonate is obtained.
5. The method according to claim 4, wherein the reaction temperature in the step S2 is 40℃to 70 ℃.
6. The method according to claim 4, wherein the neutralization reaction temperature in the step S3 is 55℃to 75 ℃.
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