CN1271183C - Method for preparing lube oil detergent of calcium nitrate in high base number - Google Patents
Method for preparing lube oil detergent of calcium nitrate in high base number Download PDFInfo
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- CN1271183C CN1271183C CN 200410037885 CN200410037885A CN1271183C CN 1271183 C CN1271183 C CN 1271183C CN 200410037885 CN200410037885 CN 200410037885 CN 200410037885 A CN200410037885 A CN 200410037885A CN 1271183 C CN1271183 C CN 1271183C
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Abstract
The present invention relates to a preparation method of a high base number detergent for calcium sulfonate lubricating oil, which comprises: sulfonate, an organic solvent, methanol and calcium hydroxide used as raw materials are circulated in a hypergravity revolving bed filler layer so as to quickly complete the process of neutralization, carbonating reaction and phase inversion under the hypergravity strengthening action; the revolving speed of the revolving bed is controlled at 200 to 1000 revolutions per minute, the flow speed ratio of carbon dioxide to liquid is 0.05 to 18: 1, and the reaction liquid is distillated under reduced pressure to remove methanol and water, diluted, deslagged in a centrifugal mode, desolvated, etc. so as to obtain the high base number detergent for calcium sulfonate lubricating oil. The present invention has the advantages of short reaction time, high efficiency, easy control of product quality and stable product performance; the obtained basic calcium carbonate granules in the center of the calcium sulfonate micelle have the advantages of small particle size and even distribution, and the particle sizes are from 20 to 40 nm.
Description
Technical field
The present invention relates to a kind of preparation method of calcium sulfonate with high base number detergent for lubricating oil, also belong to the application of hypergravity field swinging bed technology in chemical reaction engineering.
Background technology
The calcium sulfonate with high base number purification agent is the main additive that I. C. engine oil is used, and it has base number height, rust-preventing characteristic is good, acid neutralization capacity is strong characteristic, is mainly used in the medium-to-high grade I. C. engine oil of modulation.Produce the calcium sulfonate with high base number purification agent at present, both at home and abroad and adopt mechanical stirring kettle formula method basically, that is: under the reactor mechanical stirring, carry out neutralization reaction, carry out technological process preparations such as carbonation reaction and phase inversion with Bubbling method with sulfonated petro-leum (or synthesising sulfonate) and calcium hydroxide.Because traditional still formula method is produced the influence that is subjected to mechanical stirring homogeneity and bubbling contact reacts time difference, there is following shortcoming in this method: provide the carbonate particle diameter of basicity to distribute wide, particle diameter is big (being generally 20-120nm), grade poor repeatability between criticizing and criticizing, quality product is wayward, and technology is amplified difficulty, long reaction time, efficient is lower, and the raw material consumption amount is big, and energy consumption is high.
Hypergravity field swinging bed technology is the reinforcing mass transfer process greatly, applied research in field of chemical engineering in recent years makes important progress, 95105343.4) etc. particularly (patent No.: series of patents proposes to carry out the chemosynthesis of nano particle with hypergravity field swinging bed device, and hypergravity field swinging bed The Application of Technology is exploited to the chemical reaction process field from separation, resolving for the Chinese patent " preparation method of ultrafine particle " (application number 95105344.2) that proposes of the applicant (Beijing University of Chemical Technology) and " preparation method of calcium carbonate superfine powder ".In above-mentioned patented method, hypergravity swinging bed device all is to be used for the precipitin reaction system, and single step reaction is prepared nano particle.And for preparation calcium sulfonate with high base number purification agent, need carry out complicated reaction process such as neutralization reaction, carbonating, phase inversion, the microcosmic of high-gravity rotating bed great reinforcement reaction mass mix and the condition of mass transfer under, the control of the neutralization reaction speed of material and carbonating, phase inversion process and coupling etc. all are the technological difficulties of needs solution.
Summary of the invention
Distribute wide in order to overcome traditional still formula method production carbonate particle diameter, particle diameter is bigger, long reaction time, quality product is wayward, problems such as efficient is lower, the present invention proposes the novel method that a kind of hypergravity legal system is equipped with the calcium sulfonate with high base number detergent for lubricating oil, this method has solved the neutralization reaction speed of material under the hypergravity condition, technical problems such as the control of carbonating and phase inversion process and coupling, in hypergravity swinging bed device, finished neutralization reaction, carbonating, a plurality of reaction process such as phase inversion, it is little and be evenly distributed to prepare the calcium carbonate granule particle diameter, the calcium sulfonate with high base number detergent for lubricating oil of controllable product quality.
Main contents of the present invention:
Main points of the present invention are to be raw material with sulfonate, organic solvent, calcium hydroxide, methyl alcohol, neutralize under high-gravity rotating bed strengthening effect, carbonation reaction and phase inversion process.The main technique step is: sulfonate, organic solvent, calcium hydroxide, methanol mixed suspension are circulated in the rotating bed packing layer, begin simultaneously to heat up, the rotating speed of rotating bed is controlled at 100-1000 rev/min, after temperature reaches preset temperature, rotating bed feeds carbon dioxide, in the rotating bed packing layer, carry out carbonation reaction, the flow of carbon dioxide gas speed that control enters rotating bed and the ratio of circulating liquid flow velocity are in the 0.05-18 scope, so that neutralization reaction speed, carbonating and phase inversion process are complementary.Change decision reaction and phase inversion terminal point according to system temperature, when the temperature of system when curve reaches predetermined phase inversion terminal point over time, stop logical carbonic acid gas, reaction solution is emitted, by post-processing steps such as underpressure distillation dealcoholysis water, dilution, centrifugal slagging-off, desolventizings, obtain the calcium sulfonate with high base number detergent for lubricating oil.
When above-mentioned carbonation reaction, the flow of carbon dioxide gas speed that control enters rotating bed is 0.1～9m/s, and the circulating liquid flow velocity is 0.5～2m/s.
Above-mentioned neutralization reaction, carbonating and phase inversion temperature scope are 20-70 ℃.
Above-mentioned carbonation reaction and phase inversion time are 20-60 minute.
Above-mentioned sulfonate is mahogany acid ammonium or synthetic ammonium sulphonate.
Effect of the present invention:
The present invention makes reaction system that neutralization reaction take place under high-gravity rotating bed strengthening effect fast, and the neutral calcium sulfonate of generation forms anti-phase water in oil microemulsion in organic solvent; Under high-gravity rotating bed intensified condition, reaction generates nano-calcium carbonate, enters the microemulsion center under methyl alcohol and ammonia effect, finishes the phase inversion process again for calcium hydroxide and carbonic acid gas.Reaction times shortens more than 50% than traditional still formula method, and the basic carbonate calcium grain diameter at calcium sulphonate micella center is little and be evenly distributed, and particle diameter is 20～40nm.The electromicroscopic photograph of gained as shown in Figure 3.
Present method prepares processing condition such as rotor speed that performances such as the base number of calcium sulfonate with high base number detergent for lubricating oil and viscosity can be by changing rotating bed, vapour-liquid ratio, temperature of reaction, reaction times and regulates, the high base number calcium mahogany sulfonate detergent for lubricating oil of preparation, base number is generally at 290-310mgKOH/g, and kinematic viscosity (100 ℃) is less than 100mm
2/ s, product are the bright liquid of red-brown, and quality product can be controlled, stable performance.
The processing step of the present invention's exploitation is simple, and required equipment takes up an area of less, raw material consumption is few, and productive rate and production efficiency height easily amplify.
Description of drawings:
Fig. 1 is preparation technology's schematic flow sheet of the present invention.
Fig. 2 is the calcium sulfonate with high base number detergent for lubricating oil electromicroscopic photograph that traditional still formula paddling process is produced.
Fig. 3 is the calcium sulfonate with high base number detergent for lubricating oil electromicroscopic photograph that the present invention produces.
Embodiment:
As shown in Figure 4: with sulfonated petro-leum or synthetic sulfonate, organic solvent, calcium hydroxide, the methanol mixed reaction mass is poured in the steel basin 1, the configuration and the traditional method of mixed solution are similar, general sulfonate concentration is 20%-40%, after the short period of time stirring, open steel basin liquid exit valve 2, use under the effect of pump 3 in liquid circulation, enter the rotating bed from the fluid inlet 6 of rotating bed 7 by liquid meter 5 and to circulate, the size of flow rate of liquid is regulated by flow control valve 4, the control flow velocity is in 0.5～2m/s scope, the rotating speed of rotating bed is controlled at 100-1000 rev/min, and the material that comes out from rotating bed material mouth 8 is through steel basin liquid-inlet valve 9 (guiding fluid valve 10 cuts out), enter steel basin again and circulate, begin simultaneously to heat up, temperature is controlled at 20-70 ℃, after temperature reaches preset temperature, finish the neutralization reaction process, reaction mass is strengthened neutralization reaction in the rotating bed packing layer, and the neutral calcium sulfonate of generation forms anti-phase water in oil microemulsion in organic solvent; Under this preset temperature, rotating bed feeds carbon dioxide, in packing layer, begin carbonation reaction, carbon dioxide 12 is entered the rotating bed from entering the mouth by gas meter 11 control, its flow velocity is 0.1～9m/s, and calcium hydroxide and carbonic acid gas are under high-gravity rotating bed intensified condition, and reaction generates nano-calcium carbonate, under methyl alcohol and ammonia effect, enter the microemulsion center, finish the phase inversion process fast.When the temperature of system when curve reaches certain value over time, reaction and phase inversion reach terminal point, and this time period needs 20-60 minute approximately, stop logical carbonic acid gas after reaching terminal point, and reaction solution is emitted, and reacted residual gas is discharged by pneumatic outlet 13.The temperature of whole system is regulated by the water temperature of digital thermostat 17 control Water Tanks with Temp.-controlled 18.Reaction solution obtains the glue compound of nano-calcium carbonate and neutral calcium sulfonate, that is: high base number calcium mahogany sulfonate detergent for lubricating oil by post-processing steps such as underpressure distillation dealcoholysis water, dilution, centrifugal slagging-off, desolventizings.
In above-mentioned neutralization reaction and carbonation reaction and phase inversion process, hypergravity all plays an important role in the neutralization of granules preparation, phase inversion and mahogany acid ammonium.The rotating speed of vapour-liquid ratio and hypergravity machine controlling the mahogany acid ammonium in and the formation speed and the phase inversion speed of speed, lime carbonate.These three condition mutual restriction, influence each other, determining to prepare the quality of used time and product, importantly: enter high-gravity rotating bed gas and liquid feeding speed ratio (gas/liquid ratio) and rotating bed rotating speed by control, make it to be complementary with temperature of reaction, reaction times, can regulate performances such as the base number of calcium sulphonate detergent for lubricating oil and viscosity, thus the control quality product.The rotating speed that the rotating speed of rotating bed is regulated motor 14 by frequency modulation speed change instrument 15 is realized.
Above-mentioned flow process also can be taked to close steel basin liquid-inlet valve 9, opens valve 10, and material will directly circulate in rotating bed without steel basin and react and phase inversion.
Embodiment 1: with 3000 gram content is the mahogany acid ammonium of 30-35%, 995 gram calcium hydroxides, 4000 gram organic solvents, 600 gram methyl alcohol, pour into after the mixing in the circulation tank 1 and use under the effect of pump 3 in liquid circulation, enter the rotating bed from rotating bed fluid inlet 6 by liquid meter 5, shut-off valve 10, open valve 9, reaction mass is circulated in rotating bed by circulation tank, the liquid circulation flow velocity is 2m/s, and begin to heat up, when temperature reaches 55 ℃, press gas/liquid ratio 0.05 and feed carbon dioxide, the rotating speed of rotating bed is 450rpm, reacts and emits reactant after 50 minutes, through underpressure distillation dealcoholysis water, solvent cut, centrifugal slagging-off, after a series of processing such as underpressure distillation desolventizing, obtaining base number is 300mgKOH/g, and kinematic viscosity (100 ℃) is 70mm
2/ s, active principle content are 52%, and turbidity is the high-performance high base number calcium mahogany sulfonate detergent for lubricating oil of 20JTU, and the reaction times shortens 60% at least than traditional still formula method, and the carbonic acid gas consumption reduces 30%, and calcium utilization improves 25%, and the quantity of slag reduces 30%.
Embodiment 2: with 4000 gram content is the mahogany acid ammonium of 30-35%, 1330 gram calcium hydroxides, 4984 gram organic solvents, 1200 gram methyl alcohol, pour in the circulation tank after the mixing, the liquid circulation mode is with embodiment 1, the liquid circulation flow velocity is 0.5m/s, and begin to heat up, when temperature reaches 50 ℃, press gas/liquid ratio 18 and feed carbon dioxide, the rotating speed of rotating bed is 800rpm, react and emit reactant after 30 minutes, through underpressure distillation dealcoholysis water, centrifugal slagging-off, after a series of processing such as underpressure distillation desolventizing, obtaining base number is 310mgKOH/g, and kinematic viscosity (100 ℃) is 50mm
2/ s, active principle content are 54%, and turbidity is the high-performance high base number calcium mahogany sulfonate detergent for lubricating oil of 15JTU, and the reaction times shortens 75% at least than traditional still formula method, and the carbonic acid gas consumption reduces 40%, and calcium utilization improves 30%, and the quantity of slag reduces 31%.
Embodiment 3: with 4000 gram content is 35%40% mahogany acid ammonium, 1330 gram calcium hydroxides, 4984 gram organic solvents, 1200 gram methyl alcohol, pour in the circulation tank after the mixing, use under the effect of pump 3 in liquid circulation, enter the rotating bed from rotating bed fluid inlet 6 by liquid meter 5, shut-off valve 9 then, open valve 10 and make reaction mass directly circulation in rotating bed, the liquid circulation flow velocity is 1m/s, and begin to heat up, when temperature reaches 40 ℃, press gas/liquid ratio 9 and feed carbon dioxide, the rotating speed of rotating bed is 900rpm, reacts and emits reactant after 45 minutes, through underpressure distillation dealcoholysis water, centrifugal slagging-off, after a series of processing such as underpressure distillation desolventizing, obtaining base number is 290mgKOH/g, and kinematic viscosity (100 ℃) is 85mm
2/ s, active principle content are 50%, and turbidity is the high-performance high base number calcium mahogany sulfonate detergent for lubricating oil of 25JTU, and the reaction times shortens 65% at least than traditional still formula method, and the carbonic acid gas consumption reduces 35%, and calcium utilization improves 40%, and the quantity of slag reduces 40%.
Embodiment 4: be mahogany acid ammonium, 995 gram calcium hydroxides, 4000 gram organic solvents, the 750 gram methyl alcohol of 35-40% with 3000 gram content, pour in the circulation tank after the mixing, liquid circulation flow velocity and mode are with embodiment 3, and begin to heat up, when temperature reaches 45 ℃, press gas/liquid ratio 5 and feed carbon dioxide, the rotating speed of rotating bed is 100rpm, react and emit reactant after 60 minutes, after a series of processing such as underpressure distillation dealcoholysis water, centrifugal slagging-off, underpressure distillation desolventizing, obtaining base number is 295mgKOH/g, and kinematic viscosity (100 ℃) is 95mm
2/ s, active principle content are 53%, and turbidity is the high-performance high base number calcium mahogany sulfonate detergent for lubricating oil of 40JTU, and the reaction times shortens 50% at least than traditional still formula method, and the carbonic acid gas consumption reduces 25%, and calcium utilization improves 25%, and the quantity of slag reduces 25%.
Embodiment 5: be synthetic ammonium sulphonate, 995 gram calcium hydroxides, 4000 gram organic solvents, the 750 gram methyl alcohol of 35-4O% with 3000 gram content, pour into after the mixing in the circulation tank 1, liquid circulation flow velocity and mode are with embodiment 4, and begin to heat up, when temperature reaches 45 ℃, press gas/liquid ratio 9 and feed carbon dioxide, the rotating speed of rotating bed is 1000rpm, react and emit reactant after 35 minutes, after a series of processing such as underpressure distillation dealcoholysis water, centrifugal slagging-off, underpressure distillation desolventizing, obtaining base number is 325mgKOH/g, and kinematic viscosity (100 ℃) is 95mm
2/ s, active principle content are 58%, and turbidity is the high-performance high base number calcium mahogany sulfonate detergent for lubricating oil of 40JTU, and the reaction times shortens 70% at least than traditional still formula method, and the carbonic acid gas consumption reduces 40%, and calcium utilization improves 25%, and the quantity of slag reduces 25%.
Claims (2)
1, a kind of preparation method of calcium sulfonate with high base number detergent for lubricating oil, with sulfonate, organic solvent, methyl alcohol, calcium hydroxide is raw material, comprise neutralization reaction, prepared such as carbonation reaction and phase inversion process, it is characterized in that, under high-gravity rotating bed strengthening effect, finish neutralization, carbonation reaction and phase inversion process: with sulfonate, organic solvent, calcium hydroxide, methanol mixed suspension circulates in high-gravity rotating bed packing layer, begin simultaneously to heat up, the rotating speed of rotating bed is controlled at 100-1000 rev/min, after temperature reaches predetermined temperature of reaction, rotating bed feeds carbon dioxide, the flow of carbon dioxide gas speed that control enters rotating bed and the ratio of circulating liquid flow velocity are in 0.05～18 scope, carbonating and phase inversion temperature of reaction are 20-70 ℃, reaction times is 20-60 minute, stop logical carbonic acid gas then, reaction solution is emitted, by underpressure distillation dealcoholysis water, dilution, centrifugal slagging-off, post-processing steps such as desolventizing, obtain the calcium sulfonate with high base number detergent for lubricating oil, described sulfonate is mahogany acid ammonium or synthetic ammonium sulphonate.
2, the preparation method of calcium sulfonate with high base number detergent for lubricating oil according to claim 1 is characterized in that, the flow of carbon dioxide gas speed that enters rotating bed is 0.1～9m/s, and flow rate of liquid is 0.5～2m/s.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410037885 CN1271183C (en) | 2004-05-13 | 2004-05-13 | Method for preparing lube oil detergent of calcium nitrate in high base number |
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| CN 200410037885 CN1271183C (en) | 2004-05-13 | 2004-05-13 | Method for preparing lube oil detergent of calcium nitrate in high base number |
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| CN1271183C true CN1271183C (en) | 2006-08-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101372522B (en) * | 2007-08-24 | 2010-09-08 | 北京化工大学 | Method and apparatus for removing polymer volatile component |
| CN101451087B (en) * | 2007-12-04 | 2011-01-12 | 中国石油天然气股份有限公司 | Method for preparing lubricant oil metal detergent |
| CN106187827B (en) * | 2016-07-13 | 2018-09-21 | 新乡市瑞丰新材料股份有限公司 | A kind of preparation method of sulfonate |
| CN113831267A (en) * | 2021-09-08 | 2021-12-24 | 江苏澳润新材料有限公司 | Production process capable of improving purity of sulfonate |
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