CN103694148B - A kind of production method of low alkali value sulfonate detergent - Google Patents
A kind of production method of low alkali value sulfonate detergent Download PDFInfo
- Publication number
- CN103694148B CN103694148B CN201210367772.XA CN201210367772A CN103694148B CN 103694148 B CN103694148 B CN 103694148B CN 201210367772 A CN201210367772 A CN 201210367772A CN 103694148 B CN103694148 B CN 103694148B
- Authority
- CN
- China
- Prior art keywords
- low alkali
- sulfonic acid
- alkali value
- hydroxide
- sulfonate detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to the production method of a kind of low alkali value sulfonate detergent；By containing 40～60% weight flux oil the sulfonic acid of 100 weight portions, 5～10 weight portion metal-oxide or the metal hydroxides of 20～50 weight portions and water mix homogeneously after, metallization reaction is carried out within room temperature to 100 DEG C, then expansion drying is carried out, and it is refined to carry out slagging-off, low alkali value sulfonate product that obtain appearance transparent, that oily total base number is less than 50mgKOH/g；The method technical process is simple, not only need not solvent recovery process step, and synthesis yield can reach 90%(m/m) more than, one-pot utilization rate is also up to 90%(t/m3More than), it it is a kind of high efficiency environment-friendly type production method of preparing low alkali value sulfonate detergent.
Description
Technical field
The present invention relates to the production method of a kind of sulfonate detergent, a kind of high efficiency prepares the environment-friendly type production method of low alkali value sulfonate detergent, belongs to oil dope field.
Background technology
Low alkali value sulfonate has an extremely excellent function such as peace and quiet and antirust to engine surface, but also the most overbased sulfonate detergent of base number high base number in can synthesizing further, it is one of sulfonate detergent series of products.
Usually by alkali, the sulfonic acid normal salt on alkali surface is constituted the active component of low alkali value sulfonate detergent with absorption or complexation.Basic component therein refers generally to metal-oxide or hydroxide.So-called " low alkali value " refers to measure the total base number (amount of perchloric acid needed for whole basic components in neutralization 1g sample) of product according to SH/T0251 or ASTMD2896 standard method, if total base number is less than 50mgKOH/g, general between 10 to 50mgKOH/g, it is low alkali value sulfonate.
Low alkali value sulfonate can utilize " double decomposition " or " direct calcification " to prepare.
Double decomposition refers to that the sulfonic acid containing flux oil is first transformed into sodium sulfonate normal salt, then, in the presence of solvent, alkaline earth metal sulfonate is become through metathesis reaction again with alkaline-earth metal (such as calcium and magnesium barium etc.) chloride, finally, the method preparing low alkali value sulfonate through technical processs such as post processing 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 base number prepared is on the low side, and raw material availability is low, and synthesis yield is low, and production efficiency is lower.
CN200910011706,7 disclose in the presence of solvent, utilize double decomposition, use refined sulfonic acid to prepare the total base number sulfonate method less than 10mgKOH/g
Directly calcification refers in the presence of solvent, accelerator, and the technical process such as the sulfonic acid containing flux oil and alkali or alkaline earth oxide, hydroxide react through direct metallized, post processing separation and purification is to the method preparing low alkali value sulfonate.Directly calcification operation is simple and direct, and at present, the direct calcification of general employing produces low alkali value sulfonate detergent product.
U.S.2,779,784 discloses the method preparing low alkali value sulfonate in the presence of organic solvent, alcohol, water.
U.S.4,764,295 discloses at Organic Alcohol, calcium chloride water and C1~4Carboxylic acid in the presence of prepare the method for low alkali value sulfonate.
U.S4,615,841 discloses the method preparing sulfonate in the presence of non-polar solven, alkane alcohol and water.
U.S4,279,837 discloses the method preparing sulfonate in the presence of organic solvent and alkoxide.
U.S5,804,094 discloses and is more than, with molecular weight, the method that the alkyl benzene sulphonate of 500 prepares low alkali value sulfonate in the presence of organic solvent and carboxylic acid.
U.S7,094,922 discloses and prepares the total base number low alkali value sulfonate method less than 15mgKOH/g through four processing step serializations such as reaction, separation, solvent recovery and concentrations in the presence of organic solvent (accelerator), water.
In these disclosed production low alkali value sulfonate methods, the solvent used or accelerator are the most all the Organic substances harmful to environment and human body, need ability recycling after separation and purification, not only increase energy consumption and cost, but also adding processing step, production process at least need to be made up of three parts such as metallization reaction, post processing separation and purification and solvent recovery.It addition, the use of solvent reduces the one-pot utilization rate of reaction unit, to a certain degree have impact on production efficiency.
Weighing the index of low alkali value sulfonate production efficiency in addition to yield (product weight is to flux oil, sulfonic acid, the percentage ratio of the effective raw material gross weight of metallic compound three kinds) technical indicator, one-pot utilization rate (product weight ratio to reactor volume) is also unusual one of important indicator.
Summary of the invention
It is an object of the invention to provide the production method of a kind of low alkali value sulfonate detergent, overcome the organic solvent that existing sulfonate detergent exists in process of production to reclaim, environmental protection and the problem such as production efficiency is low, the method not only technical process is simple, solvent recovery process step can be saved, one-pot utilization rate is high, can prepare the total base number low alkali value sulfonate detergent product more than 20mgKOH/g especially with the method, production yield, production efficiency are high.
The production method of sulfonate detergent of the present invention is mainly made up of metallization reaction and post processing separation and purification two part.
The production method of the sulfonate detergent that the present invention proposes is: first, by oxide or the raw material mix homogeneously such as hydroxide, oil-soluble sulfonic acid of flux oil, water, alkali or alkaline-earth metal, then, carry out metallization reaction, finally, post processing separation and purification, i.e. prepare sulfonate product.
Specifically, the sulfonate detergent that the present invention proposes can produce by the following method: first, by the sulfonic acid of 100 weight portions (containing 40～60% flux oil of weight), 5～10 weight portion metal-oxide or several raw material mix homogeneously such as water of the metal hydroxides of 20～50 weight portions and 3～30 weight portions, then, metallization reaction is carried out in certain temperature range, then expansion drying is carried out, and it is refined to carry out slagging-off, transparent, the oily liquids obtained is low alkali value sulfonate product of the present invention.
The 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 condensation substance (sulfonic group is on aromatic ring) etc., it is primarily referred to as by alkyl substituted, mahogany acid, synthesis of alkyl benzenesulfonic acid or the mixing sulfonic acid particularly obtained from petroleum distillate, accordance is combined to or both are mixed to get the substituted aromatic hydrocarbons of alkyl.According to source difference, the substituted aromatic moieties of the most each alkyl contains about 16 to 80 carbon atoms, more preferably 18 to 40 carbon atoms.
The alkali of the present invention or alkaline earth metal compound are mainly alkali or the oxide of alkaline-earth metal or hydroxide, metal is mainly lithium, sodium, potassium, magnesium, calcium, barium etc., concrete such as Lithium hydrate, sodium hydroxide potassium hydroxide, calcium hydroxide calcia magnesia barium hydroxide etc., preferably Lithium hydrate, sodium hydroxide calcium hydroxide calcium oxide or magnesium oxide, more preferably calcium hydroxide calcium oxide or magnesium oxide.
The water of the present invention in metallization reaction as accelerator.The usage amount of water is 0.7～7.5 with the mol ratio of alkali or alkaline earth metal compound usage amount
The metallization reaction temperature of the present invention is typically carried out within room temperature to 100 DEG C.Metallization reaction pressure at atmosheric pressure, carry out above or below under the pressure of air can carry out metallization reaction the most at atmosheric pressure.
The post processing separation and purification purpose of the present invention is to remove the impurity thing such as low-boiling point material and unreacted solid bits.Water components (including the water that the water added and metallization reaction generate) whole in general employing expansion drying method removing system, until moisture content is less than 0.5%, the water steamed can directly recycle.Use filter, the method such as centrifugal or sedimentation removes the solids such as bits or non-molten oil thing.Embodiment is selected 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 base number of product is high, and turbidity is low, and viscosity is little, and cleansing performance is good；Production process is simple, produces yield and one-pot utilization rate reaches more than 90%；The most there is not recovery and the environmental issue of harmful organic solvent, especially production efficiency is high.
Detailed description of the invention
The analysis of indices employing, evaluation methodology in embodiments of the invention:
1. oil product total base number algoscopy SH/T0251
2. determination of calcium content method SH/T0297
3. oil product kinematic viscosity algoscopy GB/T265
4. oil dope nephelometry SH/T0028
5. moisture content GB/T260
6. I. C. engine oil QZX experiment method SH/0180235
7. crankcase simulation test method SH/T0300
Embodiment 1
Under room temperature, 170g neutral oil, 24.5g water, 28g Calx (industrial goods, purity 95%), 230g heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, direct acid number 90.5mgKOH/g) is added successively in the there-necked flask of 1L belt stirrer, stirring, temperature of charge is 61 DEG C.Utilizing electric heating cover to heat, after 1 hour 45 minutes, material is warming up to 98 DEG C, and constant temperature stirs 20 minutes, and metallization reaction terminates.Then, continue with electric heating cover heating, moisture content is evaporated off, treats that temperature of charge rises to 118 DEG C, be passed through dry air by gas distribution tube with 200ml/min flow velocity, rise to about 150 DEG C, freeze-day with constant temperature half an hour, stop expansion drying.Recording thick product solid content is 1.2%(m/m), finally, in material, add 20g super-cell (Changbai), mix homogeneously, filter, obtain about 389.6g low alkali value calcium alkylbenzenesulfonate product.
Product test result is total base number 27.3mgKOH/g, calcium content 2.65%, turbidity 17JTU, viscosity 19.47mm2/s。
Being computed, synthesis yield (product weight centering oil, sulfonic acid, the percentage ratio of the effective raw material gross weight of Calx three kinds) is 91.0%.
Embodiment 2
Under room temperature, 375g neutral oil, 49.0g water, 57g Calx (industrial goods, purity 95%), 425g heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, direct acid number 121.4mgKOH/g) is added successively in the there-necked flask of 2L belt stirrer, stirring, temperature of charge is 60 DEG C.Utilizing electric heating cover to heat, after 2 hours 15 minutes, material is warming up to 98 DEG C, and metallization reaction terminates.Then, continue with electric heating cover heating, moisture content is evaporated off, treats that temperature of charge rises to 115 DEG C, be passed through dry air by gas distribution tube with 300ml/min flow velocity, rise to about 150 DEG C, freeze-day with constant temperature half an hour, stop expansion drying.Recording thick product solid content is 2.1%(m/m), finally, in material, add 30g super-cell (Changbai), mix homogeneously, filter, obtain about 772.5g low alkali value calcium alkylbenzenesulfonate product.
Product test result is total base number 26.7mgKOH/g, calcium content 2.55%, turbidity 16JTU, viscosity 18.75mm2/s。
Being computed, synthesis yield (product weight centering oil, sulfonic acid, the percentage ratio of the effective raw material gross weight of Calx three kinds) is 90.1%.
Embodiment 3
Under room temperature, 26909Kg neutral oil, 2840Kg water, 3558Kg Calx (industrial goods are added successively in the reactor of 53 cubic meter band stirrings, purity 95%), 15791Kg heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, directly acid number 138.8mgKOH/g), by material mix homogeneously in still, still temperature show value is 60 DEG C.Utilizing reactor heating system to be heated up by material in still, after 7 hours, rise to 97 DEG C, metallization reaction terminates.Then, intensification flash distillation, meanwhile, it is passed through dry air by the gas distribution tube of Polycondensation Reactor and Esterification Reactor with 100Kg/h flow velocity, 2 hours post-samplings, the moisture content value analyzed in still in material is 0.12%, stops logical dry air, and to record thick product solid content be 2.8%(m/m).Finally, in the material containing impurity things such as solids, add 2000Kg super-cell (Changbai), mix homogeneously, and filtered by filtration system, after adding 6000Kg neutral oil rinse-system, obtain about 48750Kg low alkali value calcium alkylbenzenesulfonate industrial goods.
Industrial products test result is total base number 29.4mgKOH/g, calcium content 2.82%, turbidity 4JTU, viscosity 15.7mm2/s。
Being computed, producing yield (product weight centering oil, sulfonic acid, the percentage ratio of the effective raw material gross weight of Calx three kinds) is 93.3%.One-pot utilization rate (product weight ratio to reactor volume) is 92%(t/m3).
Comparative example 3
Under room temperature, 26909Kg neutral oil, 1858Kg calcium chloride water (concentration 4.72%%), 1200Kg n-butyl alcohol, 1085Kg methanol, 3720Kg Calx (industrial goods are added successively in the reactor of 53 cubic meter band stirrings, purity 95%), 14800Kg heavy alkylbenzene sulfonic acid (Jinzhou company industrial goods, directly acid number 138.8mgKOH/g), warming naturally to 62 DEG C, constant temperature mixes about 3 hours.Utilize reactor heating system that material is warming up to nearly 100 DEG C, then, be passed through dry air by the gas distribution tube of Polycondensation Reactor and Esterification Reactor with 100Kg/h flow velocity and continue intensification flash distillation, until the moisture analysis value in material is 0.23%, stop logical dry air.Recording thick product solid content is 12.4%(m/m), finally, in the material that moisture content is qualified, add 8250Kg super-cell (Changbai), mix homogeneously, and filtered by filtration system, obtain 19040Kg low alkali value calcium alkylbenzenesulfonate industrial goods.
Industrial products test result is total base number 19.4mgKOH/g, calcium content 1.91%, turbidity 86JTU, viscosity 36.4mm2/s。
Being computed, producing yield (product weight centering oil, sulfonic acid, the percentage ratio of the effective raw material gross weight of Calx three kinds) is 41.9%.One-pot utilization rate (product weight ratio to reactor volume) is 36%(t/m3).
The things such as the n-butyl alcohol that steams, methanol can recycle after solvent recovering system processes.
The synthetic effect data row table 1 below of each embodiment is shown
Table 1 combined coefficient
In table 1, data show: the product total base number 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 the one-pot utilization rate of synthesis yield and commercial plant all reaches more than 90%, illustrates that the inventive method quality is good, and metallization efficiency and combined coefficient are high.
Performance evaluation
Utilizing low alkali value sulfoacid calcium production piece modulation two-stroke gasoline engine oil in embodiment to be simulated assessment analysis, result of the test row table 2 below is shown:
Table 2 evaluation result
Qualification test result shows: the cleansing performance of the low alkali value sulfoacid calcium production piece of the inventive method is preferable.
Claims (1)
1. the production method of a low alkali value sulfonate detergent, it is characterized in that: by containing 40～60% weight flux oil the sulfonic acid of 100 weight portions, 5～10 weight portion metal-oxide or the metal hydroxides of 20～50 weight portions and water mix homogeneously after, metallization reaction is carried out within room temperature to 100 DEG C, then expansion drying is carried out, and it is refined to carry out slagging-off, obtains appearance transparent, oily low alkali value sulfonate detergent；
Described sulfonic acid refers to mahogany acid；Alkyl aryl sulphonic acid；Alkyl and olefin sulfonic acid；Polyoxyethylene ether sulfonic acid；Polycyclic aromatic hydrocarbon sulfonate condensation substance；Mahogany acid, alkyl benzene sulphonate or mixing sulfonic acid, wherein, the substituted aromatic moieties of each alkyl contains 16 to 80 carbon atoms；
Described metal-oxide or hydroxide are selected from Lithium hydrate, sodium hydroxide potassium hydroxide, calcium hydroxide calcia magnesia or barium hydroxide；
The usage amount of described water is 0.7～7.5 with the mol ratio of described metal-oxide or hydroxide usage amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210367772.XA CN103694148B (en) | 2012-09-28 | 2012-09-28 | A kind of production method of low alkali value sulfonate detergent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210367772.XA CN103694148B (en) | 2012-09-28 | 2012-09-28 | A kind of production method of low alkali value sulfonate detergent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103694148A CN103694148A (en) | 2014-04-02 |
| CN103694148B true CN103694148B (en) | 2016-08-03 |
Family
ID=50355841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210367772.XA Active CN103694148B (en) | 2012-09-28 | 2012-09-28 | A kind of production method of low alkali value sulfonate detergent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103694148B (en) |
Families Citing this family (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 |
-
2012
- 2012-09-28 CN CN201210367772.XA patent/CN103694148B/en active Active
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 |
|---|
| 低碱值合成磺酸钙工艺研究;曲江;《石油炼制与化工》;20090131;第40卷(第1期);30-33页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103694148A (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rodygin et al. | An efficient metal-free pathway to vinyl thioesters with calcium carbide as the acetylene source | |
| CN103635562B (en) | Tritylation ether | |
| WO2016166421A1 (en) | Method of producing furan carboxylates from aldaric acids by using solid heterogeneous catalysts | |
| CN103987682A (en) | Process for production of acrylates from epoxides | |
| CN104603245A (en) | Tritylated alkyl aryl ethers | |
| CN103694147B (en) | A kind of preparation method of sulfonate detergent | |
| CN102770510A (en) | Method for increasing color quality and stability of fuel field of the invention | |
| US9376362B2 (en) | Method for the high-yield production of P-(R-oxy)calix[9-20] arenes | |
| CN103694148B (en) | A kind of production method of low alkali value sulfonate detergent | |
| EP2844630B1 (en) | Tritylated ethers | |
| KR102328936B1 (en) | Tetrarylmethane ethers for use as fuel and oil markers | |
| Carrera et al. | Stannylated polynorbornenes as new reagents for a clean Stille reaction | |
| Pramanik et al. | Dehydrogenative Silylation of Alcohols Under Pd‐Nanoparticle Catalysis | |
| CN101044110A (en) | Particular calixarenes method for production and use thereof | |
| Khamatnurova et al. | Poly (4-dodecylstyrene) as a phase-selectively soluble polymer support in homogeneous catalysis | |
| Hu et al. | Metal‐and Solvent‐Free Transesterification and Aldol Condensation Reactions by a Homogenous Recyclable Basic Ionic Liquid Based on the 1, 3, 5‐Triazine Framework | |
| Malysheva et al. | Facile Non‐Catalyzed Synthesis of Tertiary Phosphine Sulfides by Regioselective Addition of Secondary Phosphine Sulfides to Alkenes | |
| CN109575070B (en) | Calixarene phosphate derivative with completely eliminated upper edge and completely substituted lower edge and preparation method thereof | |
| CN102317298A (en) | Thermally switchable ruthenium initiators | |
| CN102060659A (en) | Method for preparing homoallylic alcohol | |
| JP2010235453A (en) | Method for producing platinum complex | |
| CN114805674B (en) | Polymeric phosphine ligands, transition metal complexes comprising same, preparation and use thereof | |
| CN1031757C (en) | Composition of polyalkyl-aryl methane oligoner and its preparing method | |
| CN1176120C (en) | Technology of preparing comb shaped polymer by combining atomic transfer free radical and ring opening disproportionation polymerization | |
| Ti et al. | Cyclopentanone Self-Aldol Condensation by Ball-Milling Method: Optimization Using Response Surface Methodology (RSM) and Life Cycle Assessment (LCA) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |