CN108690656A - A kind of process for purification of ester oil crude product - Google Patents
A kind of process for purification of ester oil crude product Download PDFInfo
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- CN108690656A CN108690656A CN201710218390.3A CN201710218390A CN108690656A CN 108690656 A CN108690656 A CN 108690656A CN 201710218390 A CN201710218390 A CN 201710218390A CN 108690656 A CN108690656 A CN 108690656A
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- molecular distillation
- ester
- purification
- crude product
- ester oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1062—Lubricating oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of process for purification of ester oil crude product.The process for purification of the ester oil crude product of the present invention, includes the following steps:1) the first molecular distillation and the second molecular distillation are carried out successively to ester oil crude product;2) third molecular distillation is carried out to the heavy constituent that the second molecular distillation is formed;3) nitrogen air lift is carried out to the light component that third molecular distillation is formed, obtains ester oil.The production efficiency of process for purification of the present invention is high, refined at low cost, environmentally protective, and the ester oil refined through this method is close to colourless, acid value, water satisfied related request, and ester high income.
Description
Technical field
The invention belongs to ester oil technical fields, and in particular to a kind of ester oil crude product refines
Method.
Background technology
Compared with traditional mineral lubricating oil, ester oil is with viscosity temperature characteristic is excellent, thermostability is good, volatilization
Property it is low, biodegradable, can, abrasion resistance and rub resistance miscible with mineral oil and other most of synthetic oils be good, environment
The features such as friendly, be therefore widely used in aircraft turbine engine lubricating oil, precision instrumentation oil, SYNTHETIC COMPRESSOR OIL and
The fields such as refrigerator oil.
Ester oil is typically that the temperature reaction under acidic catalyst effect forms with organic acid by alcohol, the ester of reaction
Rate is low and the residual of acidic catalyst can increase the refined difficulty of follow-up ester oil crude product.Traditional alkali cleaning
The aqueous slkali of acid stripping method, generally use 5-10wt% washs thick ester product, and thick ester can be effectively removed by neutralization reaction
The impurity such as free fatty and acidic catalyst in product, while also can decoloration be played by aqueous phase separation to a certain extent
Effect.Though this method deacidification effect is good, introduce external alkali metal impurity, may cause product ash content increase, metal from
The problems such as sub- too high levels, the electrical insulation capability of ester reduces;In addition, in refined deacidification, emulsion also easy to happen, from
And lead to problems such as aliphatic acid consumption height, ester yield relatively low.
Vacuum distillation is also used for the refined of thick ester product, and this method is removed thick by way of rough vacuum vacuum distillation
The undesirable components such as free fatty and acidic catalyst in ester product, though it is simple and practicable, however removal efficiency is low, Wu Faman
The correlated quality requirement of sufficient ester oil.In addition, vacuum distillation can also be combined further with alkali cleaning depickling, though it can carry
High deacidification effect, however cannot equally solve the problems of above-mentioned.
In recent years, the relevant report of solid absorption depickling discoloration method, this method is also utilized to be adsorbed using decolorising agent
Deacidification agent adsorption deacidification is also utilized while decoloration, though there is certain effect, however deacidification value is limited, and ester yield is relatively
It is low.It would therefore be highly desirable to which a kind of can make the ester oil after refining meet related acid value, moisture requirement, and ester high income
Process for purification.
Invention content
The present invention provides a kind of process for purification of ester oil crude product, and this method production efficiency is high, refines cost
It is low, environmentally protective, through the refined ester oil of this method close to colourless, acid value, water satisfied related request, and
Ester high income.
The present invention provides a kind of process for purification of ester oil crude product, includes the following steps:
1) the first molecular distillation and the second molecular distillation are carried out successively to ester oil crude product;
2) third molecular distillation is carried out to the heavy constituent that the second molecular distillation is formed;
3) nitrogen air lift is carried out to the light component that third molecular distillation is formed, obtains ester oil.
In the present invention, ester oil crude product is referred to as thick ester;The light component that third molecular distillation is formed
Referred to as esters intermediate products;Obtained ester oil is referred to as esters product.
The present invention does not limit ester oil crude product strictly, can be polyol ester class lubricating oil crude product etc..
In the present invention, the polyol ester class lubricating oil crude product is that esterification generates polyalcohol in the presence of a catalyst with organic acid
Esterification products.The specific type of polyalcohol and organic acid is not limited strictly, polyhydric alcohols can be such as pentaerythrite, have
Machine acid for example can be isooctyl acid;At this point, the polyol ester class lubricating oil crude product is pentaerythrite and isooctyl acid in catalyst
In the presence of esterification generate esterification products.Above-mentioned polyol ester class lubricating oil crude product can usually this field conventional method obtain
It arrives.
It is understood that in polyol ester class lubricating oil crude product other than containing main quaternary saturated ester product, also
Containing a certain amount of ternary, binary, unitary beta-unsaturated esters, while also containing a certain amount of unreacted free acid and reaction generation
Water.Therefore, the target of process for purification of the present invention is the ternary being eliminated as much as in ester oil crude product, binary, one
The water that first beta-unsaturated esters, unreacted free acid and reaction generate, to make purified product meet the matter such as corresponding acid value, moisture
Amount requires.
In the present invention, molecular distillation refers to the difference using different material molecular motion free path, to containing different material
Material detached under liquid-liquid state, can make liquid at a temperature of far below its boiling point by the difference contained by it
Substance detaches.Molecular distillation usually carries out under a high vacuum, has distillation pressure is low, heated time is short, separation degree is high etc.
Feature can not only substantially reduce the separation costs of high boiler material, and can protect the quality of heat-sensitive substance well.
In the present invention, nitrogen air lift is to use nitrogen as dielectric breakdown Primordial Qi liquid biphase equilibrium, to establish one kind
New vapor liquid equilibrium state makes a certain component in solution be desorbed since partial pressure reduces, to reach separate substance
Purpose.Nitrogen air lift has the advantage that:1) operation temperature is low, less than the boiling point under relevant pressure;2) material heated time is short,
Heat medium is more mild (above-mentioned two aspect is particularly important for higher boiling and heat sensitive material);3) industrialized production ability it is big,
Not by size limit;4) nitrogen circulation uses, and does not need additional consumption;5) heating is relatively easy to, and does not need high-temperature medium (example
Such as conduction oil, fused salt).
The present inventor has found that the molecular distillation technique that two-stage or more is used alone carries out synthesizing ester lubrication through numerous studies
Refining for oily crude product, it is unsaturated for the close ternary of the boiling point contained in ester oil crude product, binary and unitary
The quaternary ester and ternary ester, removal efficiency that ester, especially molecular weight are closer to, molecular free path difference is smaller are relatively poor;Such as
For ensure removal efficiency, certainly will need carry out more stages molecular distillation processing, it is small to which there are treating capacities, production capacity is low, yield is low,
The defects of, investment height high to equipment requirement on machining accuracy, high, less economical vacuum system investment and operating cost.Relatively, such as
Fruit only considers cellular manufacture period and the product economy of industrialization product, then undesirable components in ester oil crude product
It not can be completely removed.In addition, molecular distillation equipment must gradually open vacuum system to make equipment restore normal pressure after isolation
State can suck large quantity of air in this process, since synthetic ester lubricant molecule is polarity, easily absorbs water, be easy to cause separation
Esters oil absorbs water and causes aqueous exceeded again afterwards.Therefore, the contradiction of aqueous exceeded, separating effect and economy is synthesizing ester
The maximum difficult point that lubricating oil crude product refining method is faced.
However, the present inventor can not only overcome molecule to steam the study found that using three-level molecular distillation combination nitrogen air lift
The problem of evaporating low production efficiency, while the defect of nitrogen air lift separation accuracy difference can be overcome;Wherein, three-level molecular distillation can be with
Realize most of ternary in ester oil crude product, binary, unitary beta-unsaturated esters, unreacted free acid and reaction water
The kettle of condensation product generation residual removing and decoloration in removing, Esters oil and reaction, though the oil product after three-level molecular distillation is refined
Corresponding index request cannot be reached, however Refining times are greatly decreased, production efficiency greatly improves, product yield substantially rises
Height, energy consumption are greatly reduced;Light component after three-level molecular distillation can be removed remaining non-ideal group a small amount of by nitrogen air lift
Point, especially nitrogen air lift can keep low nitrogen flux until oil product temperature be reduced to can filling temperature, to block it is refined after
Oil product contacted with air, avoid polar synthetic ester lubricant from causing product water content exceeded because absorbing moisture in air.
That is using three-level molecular distillation combination nitrogen air lift, can overcome reduced in existing esters purification techniques acid value, moisture with
It improves product yield and the contradiction between the time is long, efficiency is low, Given this completes the present invention.
In the present invention, moisture, the boiling point that the first molecular distillation is used to remove in ester oil crude product are lower
Catalyst and unreacted organic acid;Second molecular distillation is used to remove pentaerythrite half ester and the first molecular distillation is un-cleared
Organic acid and catalyst;Third molecular distillation is for decolourizing;Those skilled in the art can select suitable each according to above-mentioned purpose
Grade molecule distillation condition.
In the concrete scheme of the present invention, the temperature of the first molecular distillation can be 170-180 DEG C, and absolute pressure can be
5.5-10Pa;The temperature of second molecular distillation can be 170-180 DEG C, and absolute pressure can be 1-5.5Pa;Third molecular distillation
Temperature can be 190-200 DEG C, absolute pressure can be 0.5-1Pa.In addition, the first molecular distillation, the second molecular distillation,
The condensation temperature of three molecular distillations all can be 15-30 DEG C;It can be according to light, heavy constituent yield and acid after each molecular distillation
Value requires to select suitable condensation temperature.
In the present invention, usual manner may be used and carry out nitrogen air lift.Specifically, third molecular distillation is formed light
Component carries out nitrogen air lift, including:
After the light component that nitrogen and third molecular distillation are formed is preheated to 175-190 DEG C respectively, send to stripper and carry out
Nitrogen air lift;Wherein, it is 0-0.5MPa to control the absolute pressure inside stripper.Formed light group of nitrogen and third molecular distillation
Dividing can counter current contacting in stripper.
The present inventor it has been investigated that, nitrogen stripping temperature is more than 190 DEG C, can cause third molecular distillation formed light group
Micro substance in point is aoxidized to increase the coloration of product, and product colour is made to become light yellow from colourless, therefore the present invention
The temperature of nitrogen air lift is controlled in 175-190 DEG C of this preference temperature scope, the acid value of esters product can be made to reach requirement,
It can guarantee that the coloration of esters product, esters product comprehensive performance are good again.
Further, the light component formed by every kilogram of third molecular distillation is passed through nitrogen with the flow of 40-80L/h;It is excellent
It is selected as 50-70L/h, such as 60L/h.
In addition, being filled with filler in stripper, the filler can be filled out for stainless steel helices, Pall ring filler, porcelain ball
Material or Raschig ring filler.More specifically, the filler can be structured packing or irregular filler, wherein structured packing can be
Stainless steel structured packing, form can be chevron-shaped formula or non-corrugated plating form;Irregular filler can be filled out for stainless steel
Material or ceramic filler, can huddle form filling, and form of bio-carrier can be Pall ring filler, Raschig ring filler, porcelain ball
Filler etc..
It is possible to further be exchanged heat to stripper overhead product, gas-liquid separation, recycle nitrogen.The nitrogen of recycling can
Cycle is used for nitrogen air lift.
Acid value≤0.05mgKOH/g of the ester oil obtained through above-mentioned process for purification;In addition, synthesizing ester moistens
Moisture≤100mg/kg of lubricating oil;Yield >=80%.
The implementation of the present invention, at least has the advantage that:
1, the method for the present invention is refined at low cost, and compared with traditional process for refining, energy consumption is substantially reduced than vacuum depickling,
The unreacting material acid purity separated simultaneously is high, can be used as the utilization of esterification feedstock circulation, thereby reduces raw material
Consumption and production cost.
2, process for purification of the invention is environmentally protective, and the technique combined using three-level molecular distillation and nitrogen air lift is eliminated
Traditional alkali cleaning washing step, does not generate the three wastes.
3, process for purification of the invention, since operating pressure and temperature are relatively low in separation process, heated time is short, product
Molecular structure is kept complete in separation process, and obtained product color is good, close to colourless;In addition, the method for the present invention will not be because
It introduces impurity and influences the quality of esters product.
4, process for purification processing operation time of the invention is short, efficient, can ensure simultaneously purified product acid value and
Moisture, wherein acid value≤0.05mgKOH/g, moisture≤100mg/kg, in addition product yield >=80%.
Description of the drawings
Fig. 1 is the process flow chart of the ester oil crude product refining method of an embodiment of the present invention.
Symbol description:
1:Thick ester storage tank;2:First order molecular distillation equipment;3:Second level molecular distillation equipment;4:Third level molecular distillation
Equipment;5:Intermediate products storage tank;6:Stripper;7:Esters product storage tank;R1:Most of isooctyl acid and catalyst;D1:Through first
The thick ester of depickling that molecular distillation is formed;R2:Most of half fat and a small amount of acid;D2:After the second molecular distillation removes half ester
Thick ester;R3:Esters intermediate products after third level molecular distillation decoloration;D3:Pigment impurity.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
Technical solution in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of the every other embodiment that is obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment is using pentaerythrite and the isooctyl acid esterification products that esterification generates in the presence of a catalyst as conjunction
At lubricating oil in esters crude material, acid value 12.01mgKOH/g is stored in thick ester storage tank 1;The technique of thick ester process for purification
Flow is as shown in Figure 1, purification step is as follows:
1, the first molecular distillation
Ester oil crude product in thick ester storage tank 1 is pumped into first order molecular distillation equipment 2 and carries out first point
Son distillation, wherein the vapo(u)rizing temperature for controlling the first molecular distillation is 170 DEG C, condensation temperature is 30 DEG C, absolute pressure 7.4Pa,
To remove the most of isooctyl acid and catalyst (i.e. R1) in ester oil crude material, obtain steaming through the first molecule
Evaporate the thick ester D1 of the depickling to be formed.Wherein, R1 yields are 6.22%, and color and luster is light yellow;Thick ester D1 yields are 93.78%, color and luster
For yellow, acid value 1.67mgKOH/g.
2, the second molecular distillation
The thick ester D1 of depickling, which is then pumped in second level molecular distillation equipment 3, carries out the second molecular distillation, wherein controlling
The vapo(u)rizing temperature of two molecular distillations is 170 DEG C, and condensation temperature is 15 DEG C, absolute pressure 5.5Pa, further removing most of half
Fat and a small amount of acid (i.e. R2) obtain the thick ester D2 after the second molecular distillation removes half ester.Wherein, R2 yields are 5.87%,
Color and luster is colourless;Thick ester D2 yields are 94.13%, and color and luster is yellow, acid value 0.083mgKOH/g.
3, third molecular distillation
Thick ester D2 is then pumped to progress third molecular distillation in third level molecular distillation equipment 4, wherein control third point
The vapo(u)rizing temperature of son distillation is 195 DEG C, and condensation temperature is 15 DEG C, absolute pressure 0.52Pa, further removes pigment impurity (i.e.
D3), the esters intermediate products R3 after third level molecular distillation is decolourized is obtained, intermediate products storage tank 5 is stored in.Wherein, D3 is received
Rate is 3.63%, and color and luster is brown;R3 yields are 96.07%, and color and luster is colourless, acid value 0.085mgKOH/g.
4, nitrogen air lift
Esters intermediate products R3, is then preheated to by the stainless steel structured packing that corrugated plating form is loaded in stripper 6
180 DEG C, distributor is passed through by 6 top of stripper;Meanwhile nitrogen is preheated to 180 DEG C, by every kg light components with the stream of 60L/h
Amount is passed through stripper 6 by 6 bottom of stripper;Wherein, the absolute pressure controlled in stripper 6 is 0.1MPa, obtains synthesizing ester
Lubricating oil is stored in esters product storage tank 7.
5, nitrogen recycling utilizes
It exchanged heat, detached to 6 overhead product of stripper, the nitrogen of separation is circularly used for nitrogen air lift.
Standard is executed using GB/T7304-2014 oil product acid values, SH/T0255-92 water-in-oils execute standard to synthetic ester
The acid value and moisture of class lubricating oil are measured.The result shows that:The acid value of ester oil is 0.034mgKOH/g;Moisture
For 70mg/kg;In addition, the yield of ester oil is 83.5%.
Embodiment 2
The present embodiment is using pentaerythrite and the isooctyl acid esterification products that esterification generates in the presence of a catalyst as conjunction
At lubricating oil in esters crude material, acid value 12.01mgKOH/g is stored in thick ester storage tank 1;The technique of thick ester process for purification
Flow is as shown in Figure 1, purification step is as follows:
1, the first molecular distillation
Ester oil crude product in thick ester storage tank 1 is pumped into first order molecular distillation equipment 2 and carries out first point
Son distillation, wherein the vapo(u)rizing temperature for controlling the first molecular distillation is 175 DEG C, condensation temperature is 30 DEG C, absolute pressure 7.4Pa,
To remove the most of isooctyl acid and catalyst (i.e. R1) in ester oil crude material, obtain steaming through the first molecule
Evaporate the thick ester D1 of the depickling to be formed.Wherein, R1 yields are 8.51%, and color and luster is light yellow;Thick ester D1 yields are 91.49%, color and luster
For yellow, acid value 1.55mgKOH/g.
2, the second molecular distillation
The thick ester D1 of depickling, which is then pumped in second level molecular distillation equipment 3, carries out the second molecular distillation, wherein controlling
The vapo(u)rizing temperature of two molecular distillations is 175 DEG C, and condensation temperature is 20 DEG C, absolute pressure 5.5Pa, further removing most of half
Fat and a small amount of acid (i.e. R2) obtain the thick ester D2 after the second molecular distillation removes half ester.Wherein, R2 yields are 8.98%,
Color and luster is colourless;Thick ester D2 yields are 91.02%, and color and luster is yellow, acid value 0.077mgKOH/g.
3, third molecular distillation
Thick ester D2 subsequently enters progress third molecular distillation in third level molecular distillation equipment 4, wherein control third molecule
The vapo(u)rizing temperature of distillation is 190 DEG C, and condensation temperature is 20 DEG C, absolute pressure 0.52Pa, further removes pigment impurity (i.e.
D3), the esters intermediate products R3 after third level molecular distillation is decolourized is obtained, intermediate products storage tank 5 is stored in.Wherein, R3 is received
Rate is 1.38%, and color and luster is brown;D3 yields are 98.62%, and color and luster is colourless, acid value 0.075mgKOH/g.
4, nitrogen air lift
Pall ring filler is loaded in the form of huddling in stripper 6, esters intermediate products R3 is then preheated to 190 DEG C,
Distributor is passed through by 6 top of stripper;Meanwhile nitrogen is preheated to 190 DEG C, by every kg light components with the flow of 50L/h by vapour
6 bottom of stripper is passed through stripper 6;Wherein, the absolute pressure controlled in stripper 6 is 0.25MPa, obtains synthesizing ester lubrication
Oil is stored in esters product storage tank 7.
5, nitrogen recycling utilizes
It exchanged heat, detached to 6 overhead product of stripper, the nitrogen of separation is circularly used for nitrogen air lift.
Standard is executed using GB/T7304-2014 oil product acid values, SH/T0255-92 water-in-oils execute standard to synthetic ester
The acid value and moisture of class lubricating oil are measured.The result shows that:The acid value of ester oil is 0.029mgKOH/g;Moisture
For 55mg/kg;The yield of ester oil is 80.5%.
Embodiment 3
The present embodiment is using pentaerythrite and the isooctyl acid esterification products that esterification generates in the presence of a catalyst as conjunction
At lubricating oil in esters crude material, acid value 12.01mgKOH/g is stored in thick ester storage tank 1;The technique of thick ester process for purification
Flow is as shown in Figure 1, purification step is as follows:
1, the first molecular distillation
Ester oil crude product in thick ester storage tank 1 is added into first order molecular distillation equipment 2 and carries out first
Molecular distillation, wherein the vapo(u)rizing temperature for controlling the first molecular distillation is 180 DEG C, condensation temperature is 30 DEG C, absolute pressure 10Pa,
To remove the most of isooctyl acid and catalyst (i.e. R1) in ester oil crude material, obtain steaming through the first molecule
Evaporate the thick ester D1 of the depickling to be formed.Wherein, R1 yields are 9.69%, and color and luster is light yellow;Thick ester D1 yields are 90.31%, color and luster
For yellow, acid value 1.89mgKOH/g.
2, the second molecular distillation
The thick ester D1 of depickling, which is subsequently entered, carries out the second molecular distillation in second level molecular distillation equipment 3, wherein controlling second
The vapo(u)rizing temperature of molecular distillation is 180 DEG C, and condensation temperature is 15 DEG C, absolute pressure 3Pa, further most of half fat of removing with
A small amount of acid (i.e. R2) obtains the thick ester D2 after the second molecular distillation removes half ester.Wherein, R2 yields are 5.45%, color and luster
It is colourless;Thick ester D2 yields are 94.55%, and color and luster is yellow, acid value 0.091mgKOH/g.
3, third molecular distillation
Thick ester D2 subsequently enters progress third molecular distillation in third level molecular distillation equipment 4, wherein control third molecule
The vapo(u)rizing temperature of distillation is 200 DEG C, and condensation temperature is 15 DEG C, absolute pressure 0.7Pa, further removes pigment impurity (i.e.
D3), the esters intermediate products R3 after third level molecular distillation is decolourized is obtained, intermediate products storage tank 5 is stored in.Wherein, R3 is received
Rate is 4.21%, and color and luster is brown;D3 yields are 95.79%, and color and luster is colourless, acid value 0.084mgKOH/g.
4, nitrogen air lift
Irregular porcelain ball filler is loaded in stripper 6, esters intermediate products R3 is then preheated to 180 DEG C, by stripping
6 top of tower is passed through distributor;Meanwhile nitrogen is preheated to 180 DEG C, by every kg light components with the flow of 70L/h by 6 bottom of stripper
Portion is passed through stripper 6;Wherein, the absolute pressure controlled in stripper 6 is 0.5MPa, obtains ester oil, is stored in
Esters product storage tank 7.
5, nitrogen recycling utilizes
It exchanged heat, detached to 6 overhead product of stripper, the nitrogen of separation is circularly used for nitrogen air lift.
Standard is executed using GB/T7304-2014 oil product acid values, SH/T0255-92 water-in-oils execute standard to synthetic ester
The acid value and moisture of class lubricating oil are measured.The result shows that:The acid value of ester oil is 0.038mgKOH/g;Moisture
For 62mg/kg;The yield of ester oil is 80%.
Embodiment 4
The present embodiment is using pentaerythrite and the isooctyl acid esterification products that esterification generates in the presence of a catalyst as conjunction
At lubricating oil in esters crude material, acid value 12.01mgKOH/g is stored in thick ester storage tank 1;The technique of thick ester process for purification
Flow is as shown in Figure 1, purification step is as follows:
1, the first molecular distillation
Ester oil crude product in thick ester storage tank 1 is added into first order molecular distillation equipment 2 and carries out first
Molecular distillation, wherein the vapo(u)rizing temperature for controlling the first molecular distillation is 170 DEG C, condensation temperature is 15 DEG C, and absolute pressure is
5.5Pa obtains to remove the most of isooctyl acid and catalyst (i.e. R1) in ester oil crude material through first
The thick ester D1 of depickling that molecular distillation is formed.Wherein, R1 yields are 5.65%, and color and luster is light yellow;Slightly ester D1 yields are
94.35%, color and luster is yellow, acid value 1.90mgKOH/g.
2, the second molecular distillation
The thick ester D1 of depickling, which is subsequently entered, carries out the second molecular distillation in second level molecular distillation equipment 3, wherein controlling second
The vapo(u)rizing temperature of molecular distillation is 170 DEG C, and condensation temperature is 15 DEG C, absolute pressure 5.5Pa, further most of half fat of removing
With a small amount of acid (i.e. R2), the thick ester D2 after the second molecular distillation removes half ester is obtained.Wherein, R2 yields are 7.25%, color
Pool is colourless;Thick ester D2 yields are 92.75%, and color and luster is yellow, acid value 0.112mgKOH/g.
3, third molecular distillation
Thick ester D2 subsequently enters progress third molecular distillation in third level molecular distillation equipment 4, wherein control third molecule
The vapo(u)rizing temperature of distillation is 195 DEG C, and condensation temperature is 15 DEG C, absolute pressure 1.0Pa, further removes pigment impurity (i.e.
D3), the esters intermediate products R3 after third level molecular distillation is decolourized is obtained, intermediate products storage tank 5 is stored in.Wherein, R3 is received
Rate is 4.56%, and color and luster is brown;D3 yields are 95.44%, and color and luster is colourless, acid value 0.081mgKOH/g.
4, nitrogen air lift
Regular non-corrugated plating form stainless steel helices is loaded in stripper 6, is then preheated to esters intermediate products R3
180 DEG C, distributor is passed through by 6 top of stripper;Meanwhile nitrogen is preheated to 180 DEG C, by every kg light components with the stream of 60L/h
Amount is passed through stripper 6 by 6 bottom of stripper;Wherein, the absolute pressure controlled in stripper 6 is 0.5MPa, obtains synthesizing ester
Lubricating oil is stored in esters product storage tank 7.
5, nitrogen recycling utilizes
It exchanged heat, detached to 6 overhead product of stripper, the nitrogen of separation is circularly used for nitrogen air lift.
Standard is executed using GB/T7304-2014 oil product acid values, SH/T0255-92 water-in-oils execute standard to synthetic ester
The acid value and moisture of class lubricating oil are measured.The result shows that:The acid value of ester oil is 0.048mgKOH/g;Moisture
For 80mg/kg;The yield of ester oil is 82.1%.
Embodiment 5
The present embodiment is using pentaerythrite and the isooctyl acid esterification products that esterification generates in the presence of a catalyst as conjunction
At lubricating oil in esters crude material, acid value 12.01mgKOH/g is stored in thick ester storage tank 1;The technique of thick ester process for purification
Flow is as shown in Figure 1, purification step is as follows:
1, the first molecular distillation
Ester oil crude product in thick ester storage tank 1 is added into first order molecular distillation equipment 2 and carries out first
Molecular distillation, wherein the vapo(u)rizing temperature for controlling the first molecular distillation is 175 DEG C, condensation temperature is 25 DEG C, and absolute pressure is
5.5Pa obtains to remove the most of isooctyl acid and catalyst (i.e. R1) in ester oil crude material through first
The thick ester D1 of depickling that molecular distillation is formed.Wherein, R1 yields are 7.82%, and color and luster is light yellow;Slightly ester D1 yields are
92.18%, color and luster is yellow, acid value 0.82mgKOH/g.
2, the second molecular distillation
The thick ester D1 of depickling, which is subsequently entered, carries out the second molecular distillation in second level molecular distillation equipment 3, wherein controlling second
The vapo(u)rizing temperature of molecular distillation is 175 DEG C, and condensation temperature is 25 DEG C, absolute pressure 1.0Pa, further most of half fat of removing
With a small amount of acid (i.e. R2), the thick ester D2 after the second molecular distillation removes half ester is obtained.Wherein, R2 yields are 5.91%, color
Pool is colourless;Thick ester D2 yields are 94.09%, and color and luster is yellow, acid value 0.172mgKOH/g.
3, third molecular distillation
Thick ester D2 subsequently enters progress third molecular distillation in third level molecular distillation equipment 4, wherein control third molecule
The vapo(u)rizing temperature of distillation is 195 DEG C, and condensation temperature is 25 DEG C, absolute pressure 0.5Pa, further removes pigment impurity (i.e.
D3), the esters intermediate products R3 after third level molecular distillation is decolourized is obtained, intermediate products storage tank 5 is stored in.Wherein, R3 is received
Rate is 4.02%, and color and luster is brown;D3 yields are 95.98%, and color and luster is colourless, acid value 0.108mgKOH/g.
4, nitrogen air lift
Irregular filler stainless steel helices is loaded in stripper 6, and esters intermediate products R3 is then preheated to 175 DEG C,
Distributor is passed through by 6 top of stripper;Meanwhile nitrogen is preheated to 175 DEG C, by every kg light components with the flow of 40L/h by vapour
6 bottom of stripper is passed through stripper 6;Wherein, the absolute pressure controlled in stripper 6 is 0MPa, obtains ester oil, is stored up
It is stored in esters product storage tank 7.
5, nitrogen recycling utilizes
It exchanged heat, detached to 6 overhead product of stripper, the nitrogen of separation is circularly used for nitrogen air lift.
Standard is executed using GB/T7304-2014 oil product acid values, SH/T0255-92 water-in-oils execute standard to synthetic ester
The acid value and moisture of class lubricating oil are measured.The result shows that:The acid value of ester oil is 0.042mgKOH/g;Moisture
For 88mg/kg;The yield of ester oil is 82.05%.
Embodiment 6
The present embodiment is using pentaerythrite and the isooctyl acid esterification products that esterification generates in the presence of a catalyst as conjunction
At lubricating oil in esters crude material, acid value 12.01mgKOH/g is stored in thick ester storage tank 1;The technique of thick ester process for purification
Flow is as shown in Figure 1, purification step is as follows:
1, the first molecular distillation
Ester oil crude product in thick ester storage tank 1 is added into first order molecular distillation equipment 2 and carries out first
Molecular distillation, wherein the vapo(u)rizing temperature for controlling the first molecular distillation is 180 DEG C, condensation temperature is 20 DEG C, and absolute pressure is
8.5Pa obtains to remove the most of isooctyl acid and catalyst (i.e. R1) in ester oil crude material through first
The thick ester D1 of depickling that molecular distillation is formed.Wherein, R1 yields are 8.79%, and color and luster is light yellow;Slightly ester D1 yields are
91.21%, color and luster is yellow, acid value 0.95mgKOH/g.
2, the second molecular distillation
The thick ester D1 of depickling, which is subsequently entered, carries out the second molecular distillation in second level molecular distillation equipment 3, wherein controlling second
The vapo(u)rizing temperature of molecular distillation is 175 DEG C, and condensation temperature is 30 DEG C, absolute pressure 2.5Pa, further most of half fat of removing
With a small amount of acid (i.e. R2), the thick ester D2 after the second molecular distillation removes half ester is obtained.Wherein, R2 yields are 7.14%, color
Pool is colourless;Thick ester D2 yields are 92.86%, and color and luster is yellow, acid value 0.093mgKOH/g.
3, third molecular distillation
Thick ester D2 subsequently enters progress third molecular distillation in third level molecular distillation equipment 4, wherein control third molecule
The vapo(u)rizing temperature of distillation is 190 DEG C, and condensation temperature is 30 DEG C, absolute pressure 0.8Pa, further removes pigment impurity (i.e.
D3), the esters intermediate products R3 after third level molecular distillation is decolourized is obtained, intermediate products storage tank 5 is stored in.Wherein, R3 is received
Rate is 3.32%, and color and luster is brown;D3 yields are 96.68%, and color and luster is colourless, acid value 0.097mgKOH/g.
4, nitrogen air lift
Raschig ring filler is loaded in the form of huddling in stripper 6, esters intermediate products R3 is then preheated to 175 DEG C,
Distributor is passed through by 6 top of stripper;Meanwhile nitrogen is preheated to 175 DEG C, by every kg light components with the flow of 80L/h by vapour
6 bottom of stripper is passed through stripper 6;Wherein, the absolute pressure controlled in stripper 6 is 0.3MPa, obtains ester oil,
It is stored in esters product storage tank 7.
5, nitrogen recycling utilizes
It exchanged heat, detached to 6 overhead product of stripper, the nitrogen of separation is circularly used for nitrogen air lift.
Standard is executed using GB/T7304-2014 oil product acid values, SH/T0255-92 water-in-oils execute standard to synthetic ester
The acid value and moisture of class lubricating oil are measured.The result shows that:The acid value of ester oil is 0.045mgKOH/g;Moisture
For 75mg/kg;The yield of ester oil is 80%.
Finally it should be noted that:The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations;To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that:Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement;And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of process for purification of ester oil crude product, which is characterized in that include the following steps:
1) the first molecular distillation and the second molecular distillation are carried out successively to ester oil crude product;
2) third molecular distillation is carried out to the heavy constituent that the second molecular distillation is formed;
3) nitrogen air lift is carried out to the light component that third molecular distillation is formed, obtains ester oil.
2. process for purification according to claim 1, which is characterized in that the ester oil crude product is polyol ester
Class lubricating oil crude product.
3. process for purification according to claim 1, which is characterized in that the polyol ester class lubricating oil crude product is Ji Wusi
Alcohol and the isooctyl acid esterification products that esterification generates in the presence of a catalyst.
4. process for purification according to any one of claims 1 to 3, which is characterized in that the temperature of the first molecular distillation is 170-
180 DEG C, absolute pressure 5.5-10Pa;The temperature of second molecular distillation is 170-180 DEG C, absolute pressure 1-5.5Pa;Third
The temperature of molecular distillation is 190-200 DEG C, absolute pressure 0.5-1Pa.
5. process for purification according to claim 4, which is characterized in that the first molecular distillation, the second molecular distillation, third point
The condensation temperature of son distillation is 15-30 DEG C.
6. process for purification according to any one of claims 1 to 5, which is characterized in that light group formed to third molecular distillation
Divide and carries out nitrogen air lift, including:
After the light component that nitrogen and third molecular distillation are formed is preheated to 175-190 DEG C respectively, send to stripper and carry out nitrogen
Air lift;Wherein, it is 0-0.5MPa to control the absolute pressure inside stripper.
7. process for purification according to claim 6, which is characterized in that the light component formed by every kilogram of third molecular distillation
It is passed through nitrogen with the flow of 40-80L/h.
8. the process for purification described according to claim 6 or 7, which is characterized in that be filled with filler, the filler in stripper
For stainless steel helices, Pall ring filler, porcelain ball filler or Raschig ring filler.
9. according to any process for purification of claim 6 to 8, which is characterized in that exchanged heat to stripper overhead product,
Nitrogen is recycled in gas-liquid separation.
10. process for purification according to any one of claims 1 to 9, which is characterized in that the acid value of ester oil≤
0.05mgKOH/g, moisture≤100mg/kg, yield >=80%.
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| CN115057772A (en) * | 2022-07-12 | 2022-09-16 | 中国石油天然气集团有限公司 | Drilling fluid lubricant and preparation method thereof |
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