CN105505521A - Method for preparing silicon-based biological lubricant base oil by adopting pipeline-type recycle reactor - Google Patents
Method for preparing silicon-based biological lubricant base oil by adopting pipeline-type recycle reactor Download PDFInfo
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- CN105505521A CN105505521A CN201510932512.6A CN201510932512A CN105505521A CN 105505521 A CN105505521 A CN 105505521A CN 201510932512 A CN201510932512 A CN 201510932512A CN 105505521 A CN105505521 A CN 105505521A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/76—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing silicon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
- C10M2227/045—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes used as base material
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing silicon-based biological lubricant base oil by adopting a pipeline-type recycle reactor. The method comprises the following steps that hydrogen-containing silicone oil and fatty acid methyl ester are evenly mixed and then pumped into the pipeline-type recycle reactor, and the mixture is heated to be subjected to a reaction in the pipeline-type recycle reactor; a product generated after the reaction is completed is divided into two parts, one part returns to a reactor inlet to be recycled, and the other part serves as the product to be processed through reduced pressure distillation, and then the silicon-based biological lubricant base oil is obtained. The method is performed in the pipeline-type recycle reactor, the materials do not need to be subjected to a catalytic hydrosilylation reaction after being mixed separately, a solid catalyst and the reaction product also do not need to be separated after the reaction, continuous production is achieved, and the product quality is high.
Description
Technical field
The invention belongs to biological lubricant preparation field, relate to a kind of method preparing silica-based Biolubrication oil base oil, particularly relate to a kind of method adopting duct type recirculation reactor to prepare silica-based Biolubrication oil base oil.
Background technology
The advantages such as the good and biodegradable of the lubricity that biological lubricant has, become the environmental friendly lubricant of current main research.In prior art, many fatty acid methyl esters (biofuel) that directly adopts use as biological lubricant, but biofuel has poor thermo-oxidative stability and low temperature flowability; Therefore, in order to address these problems, chemical modification can be carried out to biofuel.Instantly be the series modified building-up reactions of epoxidation-open loop to the most cost-effective method of modifying of biofuel, this method effectively can improve thermo-oxidative stability and the low temperature flowability of biofuel.
At present, the epoxidation technique comparative maturity of vegetables oil or fatty acid ester, the technique of the isomerization reaction of epoxidized vegetable oil or epoxy aliphatic ester and alcohols generation ring opening alcoholysis also in further studying, and obtains certain achievement.(the ErhanSevimZ such as Erhan, AdhvaryuA, LiuZengshe.Chemicalmodificationofvegetableoilsforlubrica ntbasestocks [J] .AmericanSocietyofMechanicalEngineers, 2003 (5): 369-380) be that catalyzer carries out ring-opening reaction to epoxidised soybean oil at 100 DEG C with water soluble acid, reaction times is 48h, obtains open-loop products.(the HwangH such as Hwang, ErhanSZ.Syntheticlubricantbasestocksfromepoxidizedsoybea noilandGuerbetalcohols [J] .IndCropsProd, 2006,23 (3): 311-317) adopt 4 kinds of different Guerbet alcohol (C12-, C14-, C16-and C18-) and epoxy soybean oil to make catalyzer with sulfuric acid and carry out ring opening alcoholysis and transesterification reaction; Control the reaction product that reaction conditions obtains 0% (110 DEG C of stirring reaction 20h) and 100% (120 DEG C of stirring reaction 20h) transesterify respectively.(the LathiPS such as Lathi, MattiassonB.Greenapproachforthepreparationofbiodegradabl elubricantbasestockfromepoxidizedvegetableoil [J] .AppliedCatalysisB:Enviromental, 2007,69:207-212.) with Amberlyst15 (doing) for catalyzer is at 70 DEG C, stir speed (S.S.) 1000r/min carries out ring opening alcoholysis reaction, reaction times is 15h, obtains open-loop products.Tao Dehua and Li Qinghua is improving the double bond saturation isomerism etherification technology (CN101792827A) of vegetables oil antioxidant, pour point, and Yang Tiankui and Mu Ying is in a kind of production method (CN101760328A) of branched biodiesel, the method that all have employed epoxy-open loop improves oxidation stability.Excellent open-loop products is have also been obtained in the method (CN101892128A) of a kind of catalytic production of branching biological diesel by resin of Yang Tiankui and Mu Ying.
CN103789062A discloses a kind of method that biofuel prepares silica-based Biolubrication oil base oil, step is as follows: containing hydrogen silicone oil and solid catalyst mix and blend are also heated to hydrosilation reaction temperature, add fatty acid methyl ester more wherein and carry out catalyzed hydrosilation reaction, the stopped reaction when iodine number is less than 5.0g/100g, isolate solid catalyst while hot, directly underpressure distillation, finally obtains the silica-based Biolubrication oil base oil of clear again.The shortcoming such as although the method overcomes the Biolubrication oil base oil epoxidation produced in prior art and etherification technology trade effluent is many, product pour point is high, flash-point is low and viscosity temperature characteristic is poor, but it carries out catalyzed hydrosilation reaction again after first being mixed respectively by material, solid catalyst is also needed to be separated with reaction product after reaction, technique adopts gap operating, produce discontinuous, unstable product quality, manipulation strength is large, and production cost is high.
Therefore, need to develop a kind of continuous print production technique and improve the production optimizing silica-based Biolubrication oil base oil.
Summary of the invention
Gap operating is adopted for the technique of producing silica-based Biolubrication oil base oil in prior art, produce discontinuous, unstable product quality, the problem that manipulation strength is large and production cost is high, the invention provides a kind of method adopting duct type recirculation reactor to prepare silica-based Biolubrication oil base oil.The technique preparing silica-based Biolubrication oil base oil in the present invention is carried out in duct type recirculation reactor, it carries out catalyzed hydrosilation reaction after not needing material to mix respectively again, also do not need solid catalyst to be separated with reaction product after reaction, produce continuously, quality product is high.
For reaching this object, the present invention by the following technical solutions:
The invention provides a kind of method preparing silica-based Biolubrication oil base oil, described preparation method adopts duct type recirculation reactor;
Described preparation method is as follows:
Pump into after containing hydrogen silicone oil and fatty acid methyl ester are mixed in duct type recirculation reactor, in tubular circulation reactor, carry out heating react, product after having reacted is sent out and is divided into two portions, a part is back to reactor inlet and carries out recycle, and another part obtains silica-based Biolubrication oil base oil as product after underpressure distillation.
Wherein, the silica-based Biolubrication oil base oil clear obtained.
Wherein, fatty acid methyl ester is biofuel.
In the present invention, in duct type recirculation reactor, static mixer is equipped with in the front portion of duct type recirculation reactor, connects fixed-bed reactor after static mixer.
The present invention carries out in continuous pipe type recirculation reactor, by increasing recycle stock and static mixer, material can be made to mix in tubular reactor more even, improving the flow pattern of material, conversion rate of products is improved.
In the present invention, in described fixed-bed reactor, solid catalyst is housed.
Preferably, described solid catalyst is loading type Pt/ γ-Al
2o
3the combination of any one or at least two kinds in solid catalyst, Pt/ activated-carbon catalyst, Pt/ graphite catalyst or Pt/MgO catalyzer, the typical but non-limiting example of described combination has: loading type Pt/ γ-Al
2o
3the combination of solid catalyst and Pt/ activated-carbon catalyst, the combination of Pt/ activated-carbon catalyst and Pt/ graphite catalyst, the combination of Pt/ graphite catalyst and Pt/MgO catalyzer, Pt/ γ-Al
2o
3the combination etc. of solid catalyst, Pt/ activated-carbon catalyst, Pt/ graphite catalyst and Pt/MgO catalyzer.
The method of the invention, by fatty acid methyl ester and containing hydrogen silicone oil direct addition, selects supported solid catalyst to make the unsaturated carbon-carbon double bond on fatty acid methyl ester optionally adds silica-based.The product obtained combines the double dominant of biofuel and silicone oil, has zero pour low, very high thermostability, can use as environmental friendly lubricant base oil.
In the present invention, mass ratio 10:(1 ~ 10 of described fatty acid methyl ester and containing hydrogen silicone oil), such as 10:1,10:1.5,10:2,10:2.5,10:3,10:3.5,10:4,10:4.5,10:5,10:5.5,10:6,10:6.5,10:7,10:7.5,10:8,10:8.5,10:9,10:9.5 or 10:10 etc., be preferably 10:(2 ~ 8), more preferably 10:(5 ~ 7), namely guarantee that fatty acid methyl ester is excessive.
In the present invention, described containing hydrogen silicone oil has following molecular formula: R
xcl
ysiH
zwherein R is the combination of any one or at least two kinds in methyl, ethyl, phenyl, methoxy or ethoxy, described combination typical case but unrestriced example have: the combination of methyl and ethyl, the combination of ethyl and phenyl, the combination of phenyl, methoxyl group and oxyethyl group, the combination of methyl, ethyl and phenyl, the combination etc. of methyl, ethyl, phenyl, methoxyl group and oxyethyl group; X be 1,2 or 3, y be 0,1 or 2, z be 1,2 or 3, and x+y+z=4.
Wherein, the exemplary example of containing hydrogen silicone oil can be RClSiH
2, RCl
2siH, RSiH
3, R
2clSiH, R
2siH
2or R
3siH etc.
In the present invention, described containing hydrogen silicone oil and fatty acid methyl ester being mixed is uniformly mixed, and not only can adopt the mode be uniformly mixed herein, and other modes that the two can be mixed are all feasible.
Preferably, be uniformly mixed described in and carry out at stirring tank.
In the present invention, it is described that in tubular circulation reactor, carry out heating be heated to 50 ~ 100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C, be preferably 60 ~ 90 DEG C, more preferably 75 ~ 85 DEG C.
In the present invention, described carrying out in tubular circulation reactor keeps air speed to be 0.2 ~ 8h when heating reacts
-1, such as 0.2h
-1, 0.5h
-1, 1h
-1, 1.5h
-1, 2h
-1, 2.5h
-1, 3h
-1, 3.5h
-1, 4h
-1, 4.5h
-1, 5h
-1, 5.5h
-1, 6h
-1, 6.5h
-1, 7h
-1, 7.5h
-1or 8h
-1deng, be preferably 0.5 ~ 5h
-1, more preferably 1 ~ 2h
-1.
Wherein, air speed refers to the ratio of catalyst volume and entrance reaction mass volumetric flow rate.
In the present invention, the recycle ratio of described duct type recirculation reactor is 0.2 ~ 5, such as 0.2,0.5,1,1.5,2,2.5,3,3.5,4,4.5 or 5 etc., be preferably 0.5 ~ 3, more preferably 1.5 ~ 3.
Wherein, described recycle ratio is the mass ratio carrying out the material circulated in reaction after product as the material of product and Returning reactor.
In sum, a kind of concrete preparation method of method preparing silica-based Biolubrication oil base oil is as follows:
By fatty acid methyl ester and containing hydrogen silicone oil 10:(1 ~ 10 in mass ratio) mix after pump in duct type recirculation reactor, wherein, in duct type recirculation reactor, static mixer is equipped with in the front portion of duct type recirculation reactor, connect fixed-bed reactor after static mixer, in fixed-bed reactor, solid catalyst is housed;
In tubular circulation reactor, carry out being heated to 50 ~ 100 DEG C react, maintenance air speed is 0.2 ~ 8h
-1, the product after having reacted is sent out and is divided into two portions, and according to recycle ratio 0.2 ~ 5, a part is back to reactor inlet and carries out recycle, and another part obtains silica-based Biolubrication oil base oil as product after underpressure distillation.
Further, the concrete preparation method of method preparing silica-based Biolubrication oil base oil is as follows:
By fatty acid methyl ester and containing hydrogen silicone oil 10:(2 ~ 8 in mass ratio) mix after pump in duct type recirculation reactor, wherein, in duct type recirculation reactor, static mixer is equipped with in the front portion of duct type recirculation reactor, connect fixed-bed reactor after static mixer, in fixed-bed reactor, solid catalyst is housed;
In tubular circulation reactor, carry out being heated to 60 ~ 90 DEG C react, maintenance air speed is 0.5 ~ 5h
-1, the product after having reacted is sent out and is divided into two portions, and according to recycle ratio 0.5 ~ 4, a part is back to reactor inlet and carries out recycle, and another part obtains silica-based Biolubrication oil base oil as product after underpressure distillation.
Compared with prior art, the present invention has following beneficial effect:
The technique preparing silica-based Biolubrication oil base oil in the present invention is carried out in duct type recirculation reactor, it carries out catalyzed hydrosilation reaction after not needing material to mix respectively again, solid catalyst is not needed to be separated with reaction product after reaction yet, reaction process operate continuously, autoclave batch reactor is carried out under similarity condition, reaction times about 12h, and employing continuous conduit reactor of the present invention are 0.2 ~ 8h by air speed
-1calculate, the reaction times (air speed reciprocal) is 5 ~ 0.125h, and comparatively autoclave batch reactor has and significantly shortens; The transformation efficiency adopting continuous conduit reactor is 96.5 ~ 99.5%, and the transformation efficiency in prior art CN103789062A is only 93.5% ~ 95.9%; And constant product quality prepared by the present invention, cost-saving, be conducive to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is that the present invention adopts duct type recirculation reactor to prepare the process flow sheet of silica-based Biolubrication oil base oil;
Wherein, 1-stirring tank, 2-static mixer, 3-fixed-bed reactor, 4-duct type recirculation reactor.
Embodiment
Below in conjunction with several specific embodiments; exemplary illustration and help understand the present invention further; but embodiment detail is only in order to the present invention is described; do not represent the present invention and conceive lower whole technical scheme; therefore should not be construed as the technical scheme total to the present invention to limit, some are In the view of technician, and the unsubstantiality not departing from inventive concept is changed; such as simply change with the technical characteristic with same or similar technique effect or replace, all belonging to scope.
The interval value that the present invention provides, the not accurate end value of mathematical concept, and test and Selection has association when interval, suitably departs from end value and not cannot.
Following embodiment adopts technical process as shown in Figure 1 to prepare silica-based Biolubrication oil base oil, in the duct type recirculation reactor adopted, static mixer is equipped with in the front portion of duct type recirculation reactor, connect fixed-bed reactor after static mixer, in fixed-bed reactor, solid catalyst is housed.
Embodiment 1:
Pt/ γ-Al will be loaded in duct type recirculation reactor (φ 8 × 2500, stainless steel)
2o
3solid acid catalyst (40 ~ 60 order) is heated to 80 DEG C, by reaction raw materials fatty acid methyl ester and containing hydrogen silicone oil (Et
3siH) (fatty acid methyl ester/silicone oil (Et
3siH) mass ratio is 10:5) be uniformly mixed in stirring tank, with pump, raw material mixed solution is continuously pumped in duct type recirculation reactor, setting air speed 1h
-1(namely the reaction times is 1h), collect product at reactor outlet, by recycle ratio 0.5, namely the reaction product of 1/3 is recycled to reactor inlet, residue 2/3 obtains silica-based Biolubrication oil base oil as product after underpressure distillation, and the transformation efficiency of reaction outlet is 98.1%.
Under similarity condition, carry out autoclave batch reactor, the reaction times is 12h, and adopts the continuous conduit reactor described in this example, and air speed is 1h
-1, the reaction times (air speed reciprocal) is 1h, and comparatively autoclave batch reactor has and significantly shortens.
Embodiment 2:
85 DEG C are heated to, by reaction raw materials fatty acid methyl ester and containing hydrogen silicone oil (Et by loading Pt/ activated-carbon catalyst solid acid catalyst (40 ~ 60 order) in duct type recirculation reactor (φ 8 × 2500, stainless steel)
3siH) (fatty acid methyl ester/silicone oil (Et
3siH) mass ratio is 10:7) be uniformly mixed in stirring tank, with pump, raw material mixed solution is continuously pumped in duct type recirculation reactor, setting air speed 2h
-1(namely the reaction times is 0.5h), collects product, by recycle ratio 1 at reactor outlet, the reaction product of 1/2 is recycled to reactor inlet, residue 1/2 is as product discharge, and the transformation efficiency of reactor outlet is 98.3% (in silicone oil, lower same).
Under similarity condition, carry out autoclave batch reactor, reaction times 12h, and adopt the continuous conduit reactor in the present embodiment, air speed is 2h
-1, the reaction times (air speed is reciprocal) is 0.5h.
Embodiment 3:
90 DEG C are heated to, by reaction raw materials fatty acid methyl ester and containing hydrogen silicone oil (PhSiH by loading Pt/ graphite catalyst solid acid catalyst (40 ~ 60 order) in duct type recirculation reactor (φ 8 × 2500, stainless steel)
3) (fatty acid methyl ester/silicone oil (PhSiH
3) mass ratio is 10:6) be uniformly mixed in stirring tank, with pump, raw material mixed solution is continuously pumped in duct type recirculation reactor, setting air speed 2h
-1(namely the reaction times is 0.5h), by recycle ratio 2, is namely recycled to reactor inlet the reaction product of 2/3, and residue 1/3 is as product discharge, and reactor outlet transformation efficiency is 99.1%.
Autoclave batch reactor is carried out, reaction times 12h under similarity condition.And adopting the continuous conduit reactor of the present embodiment, air speed is 2h
-1, the reaction times (air speed is reciprocal) is 0.5h.
Embodiment 4:
80 DEG C are heated to, by reaction raw materials fatty acid methyl ester and containing hydrogen silicone oil (Ph by loading Pt/MgO catalyst solid acid catalyst (40 ~ 60 order) in duct type recirculation reactor (φ 8 × 2500, stainless steel)
2siH
2) (fatty acid methyl ester/silicone oil (Ph
2siH
2) mass ratio is 10:5.5) be uniformly mixed in stirring tank, with pump, raw material mixed solution is continuously pumped in duct type recirculation reactor, setting air speed 4h
-1(namely the reaction times is 0.25h), by recycle ratio 2, is namely recycled to reactor inlet the reaction product of 2/3, and residue 1/3 is as product discharge, and reactor outlet transformation efficiency is 96.7%.
Under similarity condition, carry out autoclave batch reactor, reaction times 12h, and adopt the continuous conduit reactor of the present embodiment, air speed is 4h
-1, the reaction times (air speed is reciprocal) is 0.25h.
Embodiment 5:
Pt/ graphite and Pt/ γ-Al is loaded by duct type recirculation reactor (φ 8 × 2500, stainless steel)
2o
3blended solid acid catalyst (40 ~ 60 orders, mass ratio 1:1) is heated to 60 DEG C, by reaction raw materials fatty acid methyl ester and containing hydrogen silicone oil (fatty acid methyl ester/silicone oil (Me
2siHSiHMe
2) mass ratio is 10:2) be uniformly mixed in stirring tank, with pump, raw material mixed solution is continuously pumped in duct type recirculation reactor, setting air speed 2h
-1(namely the reaction times is 0.5h), by recycle ratio 3, is namely recycled to reactor inlet the reaction product of 3/4, and residue 1/4 is as product discharge, and reactor outlet transformation efficiency is 97.3%.
Under similarity condition, carry out autoclave batch reactor, reaction times 12h, and adopt the continuous conduit reactor of the present embodiment, air speed is 2h
-1, the reaction times (air speed is reciprocal) is 0.5h.
Embodiment 6:
Except being heated to 100 DEG C in duct type recirculation reactor, containing hydrogen silicone oil is Me
2clSiH, fatty acid methyl ester/silicone oil mass ratio is 10:8, air speed 5h
-1(namely the reaction times is 0.2h), outside recycle ratio 5, the consumption of other materials and laboratory operating procedures are all in the same manner as in Example 1, and the transformation efficiency of reaction outlet is 97.5%.Under similarity condition, carrying out autoclave batch reactor, reaction times 12h, and adopt the continuous conduit reactor of the present embodiment, is 5h by air speed
-1, the reaction times (air speed is reciprocal) is 0.5h.
Embodiment 7:
Except being heated to 50 DEG C in duct type recirculation reactor, fatty acid methyl ester/silicone oil mass ratio is 10:1, air speed 0.2h
-1(namely the reaction times is 5h), outside recycle ratio 4, the consumption of other materials and laboratory operating procedures are all in the same manner as in Example 1, and the transformation efficiency of reaction outlet is 93.56%.
Under similarity condition, carrying out autoclave batch reactor, reaction times 12h, and adopt the continuous conduit reactor of the present embodiment, is 0.2h by air speed
-1, the reaction times (air speed is reciprocal) is 5h.
Embodiment 8:
Except except being heated to 75 DEG C in duct type recirculation reactor, fatty acid methyl ester/silicone oil mass ratio is 10:10, air speed 8h
-1(namely the reaction times is 0.125h), outside recycle ratio 1.5, the consumption of other materials and laboratory operating procedures are all in the same manner as in Example 1, and the transformation efficiency of reaction outlet is 92.36%.
Under similarity condition, carrying out autoclave batch reactor, reaction times 12h, and adopt the continuous conduit reactor of the present embodiment, is 8h by air speed
-1, the reaction times (air speed is reciprocal) is 0.125h.
Comparative example 1:
This comparative example is the embodiment 1 in CN103789062A:
Take the containing hydrogen silicone oil (Me of 0.5mol
2clSiH) and 0.1gPt/ gac be put in the four-hole boiling flask with condenser, agitator and thermometer, stir, reflux, be heated to 60 DEG C, add 148g (0.5mol) fatty acid methyl ester (biofuel more wherein, iodine number is 116.5g/100g), and carry out catalyzed hydrosilation reaction at such a temperature, sample from four-hole boiling flask every 1h in reaction process, measure its iodine number, the stopped reaction when iodine number is less than 5.0g/100g, is reaction end.When reaction reaches terminal, stopped reaction, while hot solid catalyst, by product again underpressure distillation take off light constituent, finally obtain silica-based Biolubrication oil base oil, the productive rate of hydrosilation reaction is 93.5%.
Comparative example 2:
Take 150g fatty acid methyl ester (biofuel: iodine number is 116.5g/100g), 100g silicone oil (Et
3siH) (fatty acid methyl ester/silicone oil (Et
3siH) mass ratio 10:6.67) and 1g solid catalyst Pt/ γ-Al
2o
3be put in the four-hole boiling flask with condenser, agitator and thermometer, stir, reflux, be heated to 90 DEG C, and carry out reaction 12h at such a temperature, sample from four-hole boiling flask, transformation efficiency is 95.8%.
Comparative example 3:
80 DEG C are heated to, by reaction raw materials fatty acid methyl ester and containing hydrogen silicone oil (Et by loading solid acid catalyst (40 ~ 60 order) in duct type recirculation reactor (φ 8 × 2500, stainless steel)
3siH) (fatty acid methyl ester/silicone oil (Et
3siH) mass ratio is 10:6.67) be uniformly mixed in stirring tank, with pump, raw material mixed solution is continuously pumped in pipeline reactor, setting air speed 1h
-1(reaction times is 1h), collect product at reactor outlet, do not circulate, sampling analysis, the productive rate of reaction is 95.9%.
The result of integrated embodiment 1-8 and comparative example 1-3 can be found out, the technique preparing silica-based Biolubrication oil base oil in the present invention is carried out in duct type recirculation reactor, it carries out catalyzed hydrosilation reaction after not needing material to mix respectively again, solid catalyst is not needed to be separated with reaction product after reaction yet, reaction process operate continuously, autoclave batch reactor is carried out under similarity condition, reaction times about 12h, and the continuous conduit reactor that the present invention adopts, be 0.2 ~ 8h by air speed
-1calculate, the reaction times (air speed reciprocal) is 5 ~ 0.125h, and comparatively autoclave batch reactor has and significantly shortens; The transformation efficiency adopting continuous conduit reactor is 96.5 ~ 99.5%, and transformation efficiency in prior art CN103789062A only; And constant product quality prepared by the present invention, cost-saving, be conducive to large-scale industrial production.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. prepare a method for silica-based Biolubrication oil base oil, it is characterized in that, described preparation method adopts duct type recirculation reactor;
Described preparation method is as follows:
Pump into after containing hydrogen silicone oil and fatty acid methyl ester are mixed in duct type recirculation reactor, in tubular circulation reactor, carry out heating react, product after having reacted is sent out and is divided into two portions, a part is back to reactor inlet and carries out recycle, and another part obtains silica-based Biolubrication oil base oil as product after underpressure distillation.
2. method according to claim 1, is characterized in that, in duct type recirculation reactor, static mixer is equipped with in the front portion of duct type recirculation reactor, connects fixed-bed reactor after static mixer.
3. method according to claim 2, is characterized in that, in described fixed-bed reactor, solid catalyst is housed;
Preferably, described solid catalyst is loading type Pt/ γ-Al
2o
3the combination of any one or at least two kinds in solid catalyst, Pt/ activated-carbon catalyst, Pt/ graphite catalyst or Pt/MgO catalyzer.
4. the method according to any one of claim 1-3, is characterized in that, mass ratio 10:(1 ~ 10 of described fatty acid methyl ester and containing hydrogen silicone oil), be preferably 10:(2 ~ 8), more preferably 10:(5 ~ 7).
5. the method according to any one of claim 1-4, is characterized in that, described containing hydrogen silicone oil has following molecular formula: R
xcl
ysiH
z, wherein R is the combination of any one or at least two kinds in methyl, ethyl, phenyl, methoxy or ethoxy; X be 1,2 or 3, y be 0,1 or 2, z be 1,2 or 3, and x+y+z=4.
6. the method according to any one of claim 1-5, is characterized in that, described containing hydrogen silicone oil and fatty acid methyl ester being mixed is uniformly mixed;
Preferably, be uniformly mixed described in and carry out at stirring tank.
7. the method according to any one of claim 1-6, is characterized in that, described in tubular circulation reactor, carry out heating be heated to 50 ~ 100 DEG C, is preferably 60 ~ 90 DEG C, more preferably 75 ~ 85 DEG C.
8. the method according to any one of claim 1-7, is characterized in that, described carrying out in tubular circulation reactor keeps air speed to be 0.2 ~ 8h when heating reacts
-1, be preferably 0.5 ~ 5h
-1, more preferably 1 ~ 2h
-1.
9. the method according to any one of claim 1-8, is characterized in that, the recycle ratio of described duct type recirculation reactor is 0.2 ~ 5, is preferably 0.5 ~ 4, more preferably 1.5 ~ 3.
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| CN114426667A (en) * | 2022-03-16 | 2022-05-03 | 江西海多化工有限公司 | Continuous preparation system and process method of narrow molecular weight MQ resin |
| CN114957666A (en) * | 2022-06-28 | 2022-08-30 | 埃夫科纳聚合物股份有限公司 | Preparation method of hydrogen-containing silicone oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112661965A (en) * | 2020-12-22 | 2021-04-16 | 埃夫科纳聚合物股份有限公司 | Preparation method of organic silicon auxiliary agent |
| CN114426667A (en) * | 2022-03-16 | 2022-05-03 | 江西海多化工有限公司 | Continuous preparation system and process method of narrow molecular weight MQ resin |
| CN114957666A (en) * | 2022-06-28 | 2022-08-30 | 埃夫科纳聚合物股份有限公司 | Preparation method of hydrogen-containing silicone oil |
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