CN103694148A - Production method of low-alkali-value sulfonate clearing agent - Google Patents
Production method of low-alkali-value sulfonate clearing agent Download PDFInfo
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- CN103694148A CN103694148A CN201210367772.XA CN201210367772A CN103694148A CN 103694148 A CN103694148 A CN 103694148A CN 201210367772 A CN201210367772 A CN 201210367772A CN 103694148 A CN103694148 A CN 103694148A
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Abstract
The invention relates to a production method of a low-alkali-value sulfonate clearing agent. The production method comprises the steps: mixing uniformly 100 parts by weight of sulfonic acid containing 40-60 wt% of a dilute oil, 5 to 10 parts by weight of a metal oxide or 20 to 50 parts by weight of a metal hydroxide and water, carrying out a metallization reaction in the temperature range of the room temperature to 100 DEG C, then carrying out flash evaporation drying, carrying out slag removal and refining, and thus obtaining the low-alkali-value sulfonate clearing agent having transparent appearance and the oily total base value of less than 50 mgKOH/g. The method has simple technological process, not only has no need of a solvent recovery technological step, but also enables the synthetic yield to reach 90% (m/m) or more, enables the single-kettle utilization rate to be up to 90% (t/m<3>) or more, and is an environmental-protection production method for high-efficiency preparation of the low-alkali-value sulfonate clearing agent.
Description
Technical field
The present invention relates to a kind of production method of sulfonate detergent, especially a kind of high-level efficiency is prepared the environment-friendly type production method of low alkali value sulfonate detergent, belongs to oil dope field.
Background technology
Low alkali value sulfonate has the extremely excellent function such as peace and quiet and antirust to Engine Surface, but also can further synthesize the middle even overbased sulfonate detergent of Jian Zhi ﹑ high base number, is one of sulfonate detergent series product.
The active principle of low alkali value sulfonate detergent is generally to consist of at the lip-deep sulfonic acid normal salt of alkali alkali and absorption or complexing.Basic component wherein refers generally to metal oxide or oxyhydroxide.So-called " low alkali value " refers to the total basicnumber (in and in 1g sample all the amount of the required perchloric acid of basic component) of measuring product according to SH/T 0251 or ASTM D2896 standard method, if total basicnumber is less than 50mgKOH/g, generally, between 10 to 50mgKOH/g, be low alkali value sulfonate.
Low alkali value sulfonate can utilize " double decomposition " or " directly calcification " to prepare.
Double decomposition refers to that the sulfonic acid that contains thinning oil is first transformed into sodium sulfonate normal salt, then, under solvent exists, again with alkaline-earth metal (as Gai ﹑ Mei ﹑ barium etc.) muriate becomes alkaline earth metal sulfonate through replacement(metathesis)reaction, finally, the method for preparing low alkali value sulfonate through technological processs such as aftertreatment separation and purifications.Double decomposition processing step is many, and operation is long, and in system, impurity is many, and separation and purification is loaded down with trivial details, and the product total basicnumber of preparing is on the low side, and raw material availability is low, and synthesis yield is low, and production efficiency is lower.
CN 200910011706,7 discloses under solvent exists, and utilizes double decomposition, adopts refining sulfonic acid to prepare the sulfonate method that total basicnumber is less than 10mgKOH/g
Directly calcification refers under solvent, promotor exist, and the sulfonic acid that contains thinning oil and alkali or alkaline earth metal oxide, oxyhydroxide pass through the method that the technological processs such as direct metallized is reacted, aftertreatment separation and purification are prepared low alkali value sulfonate.Directly calcification operation is simple and direct, at present, generally adopts direct calcification to produce low alkali value sulfonate detergent product.
U.S.2,779,784 disclose the method for preparing low alkali value sulfonate under organic solvent, alcohol, water existence.
U.S.4,764,295 disclose at Organic Alcohol, calcium chloride water and C
1~
4carboxylic acid prepare the method for low alkali value sulfonate under existing.
U.S 4,615, and 841 disclose the method for preparing sulfonate under non-polar solvent, the existence of alkane alcohol and water.
U.S 4,279, and 837 disclose the method for preparing sulfonate under organic solvent and alkoxide existence.
U.S 5,804, and 094 discloses under organic solvent and carboxylic acid exist with molecular weight and is greater than the method that 500 alkyl benzene sulphonate (ABS) is prepared low alkali value sulfonate.
U.S 7,094,922 disclose at organic solvent (promotor), water, exist lower through reaction, separated, solvent recuperation and four processing step serializations such as concentrate and prepare the low alkali value sulfonate method that total basicnumber is less than 15mgKOH/g.
In these disclosed production low alkali value sulfonate methods, solvent or the promotor of using are all to environment and the harmful organism of human body mostly, needing after separation and purification could recycling, production energy consumption and cost have not only been increased, but also having increased processing step, production process at least need be comprised of three parts such as metallization reaction, aftertreatment separation and purification and solvent recuperation.In addition, the use of solvent has reduced single still utilization ratio of reaction unit, has to a certain degree affected production efficiency.
Weigh the index of low alkali value sulfonate production efficiency except yield (per-cent of product weight to thinning oil, sulfonic acid, three kinds of effective raw material gross weights of metallic compound) technical indicator, single still utilization ratio (ratio of product weight to reactor volume) is also unusual one of important indicator.
Summary of the invention
The production method that the object of this invention is to provide a kind of low alkali value sulfonate detergent, overcome the problems such as organic solvent recovery, environmental protection and production efficiency that existing sulfonate detergent exists is in process of production low, the method not only technological process is simple, can save solvent recovery process step, single still utilization ratio is high, especially utilize the method can prepare the low alkali value sulfonate detergent product that total basicnumber is greater than 20mgKOH/g, produce yield, production efficiency is high.
The production method of sulfonate detergent of the present invention is mainly comprised of metallization reaction and aftertreatment separation and purification two parts.
The production method of the sulfonate detergent that the present invention proposes is: first, the raw materials such as the oxide compound of thinning oil, water, alkali or alkaline-earth metal or oxyhydroxide, oil-soluble sulfonic acid are mixed, then, carry out metallization reaction, finally, aftertreatment separation and purification, makes sulfonate product.
Specifically, the sulfonate detergent that the present invention proposes can be produced by the following method: first, several raw materials such as water of the sulfonic acid of 100 weight parts (containing the thinning oil of 40～60% weight), the metal oxide of 5～10 weight parts or the metal hydroxides of 20～50 weight parts and 3～30 weight parts are mixed, then, in certain temperature range, carry out metallization reaction, then carry out expansion drying, and it is refining to remove the gred, transparent, the oily liquids obtaining is low alkali value sulfonate product of the present invention.
Sulfonic acid of the present invention refers to mahogany acid (sulfonic group is on aromatic ring or naphthenic ring); Alkyl aryl sulphonic acid (sulfonic group is on aromatic ring); Alkyl and olefin sulfonic acid; Polyoxyethylene ether sulfonic acid (sulfonic group is at the oxygen ethyl end of the chain) or polycyclic aromatic hydrocarbon sulfonate condenses (sulfonic group is on aromatic ring) etc., mainly refer to be replaced by alkyl the aromatic hydrocarbons particularly replacing from petroleum fractions, alkylating aromatic hydrocarbon is synthetic or both are mixed to get alkyl and the mahogany acid, the synthesis of alkyl Phenylsulfonic acid that obtain or mix sulfonic acid.Different according to source, the aromatic ring that preferably each alkyl replaces is partly containing having an appointment 16 to 80 carbon atoms, more preferably 18 to 40 carbon atoms.
Alkali of the present invention or alkaline earth metal compound are mainly oxide compound or the oxyhydroxide of alkali or alkaline-earth metal, if master metal lithium, sodium, potassium, magnesium, calcium, barium etc., concrete as lithium hydroxide, Qing Yangization Na ﹑ potassium hydroxide, Qing Yangization Gai ﹑ Yangization Gai ﹑ Yangization Mei ﹑ hydrated barta etc., preferred lithium hydroxide, Qing Yangization Na ﹑ Qing Yangization Gai ﹑ calcium oxide or magnesium oxide, more preferably Qing Yangization Gai ﹑ calcium oxide or magnesium oxide.
Water of the present invention in metallization reaction as promotor.The mol ratio of the usage quantity of water and alkali or alkaline earth metal compound usage quantity is 0.7～7.5
Metallization reaction temperature of the present invention is generally carried out within normal temperature to 100 ℃.Metallization reaction pressure can be under barometric point, surpass or lower than carrying out under the pressure of atmosphere, preferably under barometric point, carry out metallization reaction.
Aftertreatment separation and purification object of the present invention is to remove the impurity things such as low-boiling point material and unreacted solid bits.The general expansion drying method that adopts is removed water component whole in system (comprising the water that the water that adds and metallization reaction generate), until moisture content is less than 0.5%, the water steaming can directly recycle.Adopt to filter, the method such as centrifugal or sedimentation removes solid or the non-molten oily things such as bits.In embodiment, select filter type slagging-off.
Low alkali value sulfonate detergent prepared by the method, thick product solid content is low, and metallization efficiency is high; The total basicnumber of product is high, and turbidity is low, and viscosity is little, and cleansing performance is good; Production process is simple, produces yield and single still utilization ratio and reaches more than 90%; The recovery and the environmental issue that not only do not have harmful organic solvent, especially production efficiency is high.
Embodiment
Analysis, evaluation method that in embodiments of the invention, indices adopts:
1. petroleum products total basicnumber assay method SH/T 0251
2. determination of calcium content method SH/T 0297
3. petroleum products kinematic viscosity assay method GB/T 265
4. oil dope tuurbidimetry SH/T 0028
5. moisture content GB/T 260
6. I. C. engine oil coking plate test method(s) SH/0180235
7. crankcase simulation test method SH/T 0300
Embodiment 1
Under normal temperature, in the there-necked flask of 1L belt stirrer, add 170g neutral oil, 24.5g water, 28g white lime (industrial goods, purity 95%), 230g heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, directly acid number 90.5mgKOH/g) successively, stir, temperature of charge is 61 ℃.Utilize electric heating cover heating, after 1 hour 45 minutes, material is warming up to 98 ℃, and constant temperature stirs 20 minutes, and metallization reaction finishes.Then, continue to utilize electric heating cover heating, steam except moisture content, treat that temperature of charge rises to 118 ℃, by gas distribution tube, with 200ml/min flow velocity, pass into dry air, rise to 150 ℃ of left and right, freeze-day with constant temperature half an hour, stop expansion drying.Recording thick product solid content is 1.2%(m/m), last, in material, add 20g super-cell (Changbai), mix, filter, obtain about 389.6g low alkali value calcium alkylbenzenesulfonate product.
Product test result is total basicnumber 27.3mgKOH/g, calcium contents 2.65%, turbidity 17JTU, viscosity 19.47mm
2/ s.
As calculated, synthesis yield (per-cents of product weight centering oil, sulfonic acid, three kinds of effective raw material gross weights of white lime) is 91.0%.
Embodiment 2
Under normal temperature, in the there-necked flask of 2L belt stirrer, add 375g neutral oil, 49.0g water, 57g white lime (industrial goods, purity 95%), 425g heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, directly acid number 121.4mgKOH/g) successively, stir, temperature of charge is 60 ℃.Utilize electric heating cover heating, after 2 hours 15 minutes, material is warming up to 98 ℃, and metallization reaction finishes.Then, continue to utilize electric heating cover heating, steam except moisture content, treat that temperature of charge rises to 115 ℃, by gas distribution tube, with 300ml/min flow velocity, pass into dry air, rise to 150 ℃ of left and right, freeze-day with constant temperature half an hour, stop expansion drying.Recording thick product solid content is 2.1%(m/m), last, in material, add 30g super-cell (Changbai), mix, filter, obtain about 772.5g low alkali value calcium alkylbenzenesulfonate product.
Product test result is total basicnumber 26.7mgKOH/g, calcium contents 2.55%, turbidity 16JTU, viscosity 18.75mm
2/ s.
As calculated, synthesis yield (per-cents of product weight centering oil, sulfonic acid, three kinds of effective raw material gross weights of white lime) is 90.1%.
Embodiment 3
Under normal temperature, in the reactor stirring to 53 cubic meter bands successively, add 26909Kg neutral oil, 2840Kg water, 3558Kg white lime (industrial goods, purity 95%), 15791Kg heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, direct acid number 138.8mgKOH/g), mixing of materials in still is even, and still temperature displayed value is 60 ℃.Utilize reactor heating system that material in still is heated up, after 7 hours, rise to 97 ℃, metallization reaction finishes.Then, intensification flash distillation, meanwhile, the gas distribution tube by Polycondensation Reactor and Esterification Reactor passes into dry air with 100Kg/h flow velocity, 2 hours post-samplings, analyzing the moisture content value in material in still is 0.12%, stops logical dry air, and to record thick product solid content be 2.8%(m/m).Finally, in the material that contains the impurity things such as solid, add 2000Kg super-cell (Changbai), mix, and by filtration system filters, add after 6000Kg neutral oil rinse-system, obtain about 48750Kg low alkali value calcium alkylbenzenesulfonate industrial goods.
Industrial products test result is total basicnumber 29.4mgKOH/g, calcium contents 2.82%, turbidity 4JTU, viscosity 15.7mm
2/ s.
As calculated, producing yield (per-cents of product weight centering oil, sulfonic acid, three kinds of effective raw material gross weights of white lime) is 93.3%.Single still utilization ratio (ratio of product weight to reactor volume) is 92%(t/m
3).
Comparative example 3
Under normal temperature, in the reactor stirring to 53 cubic meter bands successively, add 26909Kg neutral oil, 1858Kg calcium chloride water (concentration 4.72%%), 1200Kg propyl carbinol, 1085Kg methyl alcohol, 3720Kg white lime (industrial goods, purity 95%), 14800Kg heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, direct acid number 138.8mgKOH/g), naturally be warming up to 62 ℃, constant temperature mixes approximately 3 hours.Utilize reactor heating system that material is warming up to nearly 100 ℃, then, the gas distribution tube by Polycondensation Reactor and Esterification Reactor passes into dry air with 100Kg/h flow velocity and continues intensification flash distillation, until the moisture analysis value in material is 0.23%, stops logical dry air.Recording thick product solid content is 12.4%(m/m), last, in the qualified material of moisture content, add 8250Kg super-cell (Changbai), mix, and by filtration system filters, obtain 19040Kg low alkali value calcium alkylbenzenesulfonate industrial goods.
Industrial products test result is total basicnumber 19.4mgKOH/g, calcium contents 1.91%, turbidity 86JTU, viscosity 36.4mm
2/ s.
As calculated, producing yield (per-cents of product weight centering oil, sulfonic acid, three kinds of effective raw material gross weights of white lime) is 41.9%.Single still utilization ratio (ratio of product weight to reactor volume) is 36%(t/m
3).
The things such as the propyl carbinol steaming, methyl alcohol can recycle after solvent recovering system is processed.
The synthetic effect data rows following table 1 of each embodiment is shown
Table 1 combined coefficient
In table 1, data show: the product total basicnumber of the inventive method is high, and turbidity is low, and viscosity is little; The thick product solid content of the inventive method is less than 4%, and single still utilization ratio of synthesis yield and full scale plant all reaches more than 90%, illustrates that the inventive method quality is good, and metallization efficiency and combined coefficient are high.
Performance evaluation
Utilize low alkali value calcium sulphonate production piece modulation two-stroke gasoline engine oil in embodiment to carry out simulation evaluation analysis, test-results row following table 2 is shown:
Table 2 evaluation result
Qualification test result shows: the cleansing performance of the low alkali value calcium sulphonate production piece of the inventive method is better.
Claims (4)
1. the production method of a low alkali value sulfonate detergent, it is characterized in that: by containing the sulfonic acid of 100 weight parts of 40～60% weight thinning oils, after the metal hydroxides of the metal oxide of 5～10 weight parts or 20～50 weight parts and water mixes, within normal temperature to 100 ℃, carry out metallization reaction, then carry out expansion drying, and it is refining to remove the gred, obtain appearance transparent, oily low alkali value sulfonate detergent.
2. according to the production method of low alkali value sulfonate detergent claimed in claim 1, it is characterized in that: described sulfonic acid refers to mahogany acid; Alkyl aryl sulphonic acid; Alkyl and olefin sulfonic acid; Polyoxyethylene ether sulfonic acid; Polycyclic aromatic hydrocarbon sulfonate condenses; Mahogany acid, alkyl benzene sulphonate (ABS) or mixing sulfonic acid, wherein, the aromatic ring that each alkyl replaces is partly containing having an appointment 16 to 80 carbon atoms.
3. according to the production method of low alkali value sulfonate detergent claimed in claim 1, it is characterized in that: described alkali or the oxide compound of alkaline-earth metal or oxyhydroxide are selected from lithium hydroxide, Qing Yangization Na ﹑ potassium hydroxide, Qing Yangization Gai ﹑ Yangization Gai ﹑ magnesium oxide or hydrated barta.
4. according to the production method of low alkali value sulfonate detergent claimed in claim 1, it is characterized in that: the mol ratio of the usage quantity of described water and alkali or alkaline earth metal compound usage quantity is 0.7～7.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115247089A (en) * | 2021-04-28 | 2022-10-28 | 中国石油天然气股份有限公司 | Preparation method of low-base-number alkylbenzene sulfonate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114349A (en) * | 1994-06-22 | 1996-01-03 | 中国石油化工总公司石油化工科学研究院 | Process for preparing synthesized oil-soluble rust-preventive agent of barium sulfonate |
| US6268318B1 (en) * | 1998-03-27 | 2001-07-31 | The Lubrizol Corporation | Process for making overbased calcium sulfonate detergents using calcium oxide and a less than stoichiometric amount of water |
| CN101602696A (en) * | 2009-05-26 | 2009-12-16 | 锦州康泰润滑油添加剂有限公司 | A kind of preparation method of calcium sulfonate salt with low alkali value |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114349A (en) * | 1994-06-22 | 1996-01-03 | 中国石油化工总公司石油化工科学研究院 | Process for preparing synthesized oil-soluble rust-preventive agent of barium sulfonate |
| US6268318B1 (en) * | 1998-03-27 | 2001-07-31 | The Lubrizol Corporation | Process for making overbased calcium sulfonate detergents using calcium oxide and a less than stoichiometric amount of water |
| CN101602696A (en) * | 2009-05-26 | 2009-12-16 | 锦州康泰润滑油添加剂有限公司 | A kind of preparation method of calcium sulfonate salt with low alkali value |
Non-Patent Citations (1)
| Title |
|---|
| 曲江: "低碱值合成磺酸钙工艺研究", 《石油炼制与化工》, vol. 40, no. 1, 31 January 2009 (2009-01-31), pages 30 - 33 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115247089A (en) * | 2021-04-28 | 2022-10-28 | 中国石油天然气股份有限公司 | Preparation method of low-base-number alkylbenzene sulfonate |
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