CN101245006A - Process for producing pentaerythritol oleate - Google Patents
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Abstract
A preparation method of pentaerythrite oleate belongs to the technical field of the synthesis of the foundation oil of biological degradable lubricating oil; the invention provides an improved preparation method of pentaerythrite oleate, which adopts p-toluene sulfonic acid carried by activated carbon as catalyst, oleic acid and pentaerythritol are regarded as raw material for esterification so as to obtain primary products of the pentaerythrite oleate, then molecule distillation treatment is adopted to obtain the products of pentaerythrite oleate; the preparation method of the pentaerythrite oleate chooses economical activated carbon as the load to carry p-toluene sulfonic acid, the activated carbon can be obtained from a plurality of resources, impregnation method is used as the loading method, the method adopts the p-toluene sulfonic acid carried by activated carbon to catalyze reactions for the first time, which has the advantages of obvious catalyzing performance, the catalyst being easy to be separated from products, no acid waste water pollution being caused, and little pollution being caused to environment, and the catalyst is one of environmental-protection catalyst; the pentaerythrite oleate is beneficial for environmental protection, can prolong the service life of machines, and has good safety and renewable capacity.
Description
Technical field
A kind of preparation method of PETO adopts the technology of activated carbon supported p-methyl benzenesulfonic acid catalytic preparation PETO, belongs to biodegradable lube oil base oil synthesis technical field.
Background technology
For the friction and wear of the surface in contact that reduces by two relative movement, people have used lubricating oil.Good lubricating oil can improve the efficient of machinery, keeps machinery to work stably in a long term.Lubricating oil is made up of base oil and additive, and wherein base oil accounts for more than the 80%-90%.The main character of lubricating oil (as biological degradability, high-temperature stability, low-temperature fluidity etc.) is all by basic oil properties decision.At present, the base oil of lubricant can adopt mineral oil, vegetable and animals oils and ucon oil.Present most lube product all is to be base oil with mineral oil.There is huge pollution in mineral oil to environment, thereby will quits the stage gradually because it is non-renewable.Directly then there are shortcomings such as thermostability, oxidative stability and stability to hydrolysis difference as lubricant base with vegetable and animals oils.So people have concentrated on sight on the ucon oil (adopting the base oil of methodology of organic synthesis preparation fully).ASTM is divided into synthetic lubricant base oil three classes such as synthin, organic ester and other ucon oil.Wherein lubricating oil in esters occupies an important position and quite great proportion (80%).Synthetic ester lubricant be by organic acid and alcohol under catalyst action, esterification dehydration and obtaining.According to the ester group content of reaction product, ester class oil is divided into dibasic acid esters, polyol ester and multiple ester etc.
PETO belongs to the base oil of neopentyl polyol ester (neopentyl polyol ester is by TriMethylolPropane(TMP), tetramethylolmethane, dimethyltrimethylene glycol and straight chain or the product of branched fatty acid response) class.It has good low-temperature performance and viscosity temperature characteristic, good heat-resistant quality, oxidative stability and favorable environment protection preferably, therefore is applied in aircraft oil, automotive lubricant, air compressor machine oil and non-flame properties hydraulic pressure wet goods field widely.
China originates in the initial stage sixties for the research of esters syntholube, and at present, having worked out the polyol ester class lubricating oil has 4050,4051,4106 etc.On synthesis technique, the research that the research of China's polyol ester focuses mostly on and reacts with the direct esterification of straight chain fatty acid and polyvalent alcohol in direct, that wherein most of people study is the lipid acid (C of short carbon chain
2-C
11) with the esterification process of polyvalent alcohol.Study on the synthesis for PETO is reported then seldom.People such as Fu Tingjin, official's bodyguard dragon, Hu Wenyun utilize mixed fatty acid and the tetramethylolmethane esterification that comprises oleic acid, and catalyzer comprises sulfuric acid, solid acid catalyst and metal catalyst etc., and study on the synthesis rests on experiment of single factor, product does not have analysis.People such as Zhou Cun utilize oleic acid and tetramethylolmethane to send out and answer, and have carried out experiment of single factor and selection of catalysts, and experiment is found to make catalyzer with tin protoxide, and the catalyst quality mark is 0.8%, and temperature of reaction is at 200 ℃, and product is better.Oldly just wait the people to find to make catalyzer with metal-powder for a short time, catalyst levels is oleic 0.5%, temperature of reaction 210-220 ℃, and reaction 4h, esterification yield is more than 95%.Equally, people such as Liu Fanjia has also drawn similar conclusion.A Chinese patent has been reported a kind of synthetic method of PETO, reports, under the effect of organic acid catalyst, oleic acid and tetramethylolmethane carry out esterification, is that the high vacuum condition of 20-100pa is sloughed residual acid and obtained product in vacuum tightness then.
1963, United States Navy's proposition use temperature was-40～200 ℃ a MIL-L-23699 specification.Afterwards, be that the synthetic aircraft oil of II type medium viscosity of base oil just is widely applied on naval aircraft and the aircarrier aircraft with the polyol ester, synthesizing ester oil industrial scale is developed rapidly.Enter the seventies, esters syntholube is obtaining widespread use aspect I. C. engine oil, compressor oil, the high-speed gear wet goods rapidly.Make its output be only second to polyethers and poly--alhpa olefin in the ucon oil field, row occupy the 3rd.1987, the U.S. was consumed in 1.64 ten thousand tons of the neopentyl polyol esters of ucon oil.1.48 ten thousand tons of the neopentyl polyol ester lubricating oil that West Europe 1986 consumes.At present, production has Mobil Jet Oil II, Esso Turbo Oil 2380, a Mobil JetOil 254 etc.People such as Gerard hellion with linoleic acid content after the sunflower seed oil more than 65% carries out esterification, successively by isomerization, interpolymerization, hydrogenation and transesterify (dibutoxy tin 0.05%, methyl esters/TriMethylolPropane(TMP)=3.1: 1,200-220 ℃, 5h) obtain the polyvalent alcohol side chain fatty acid ester.The product pour point is lower than-53 ℃, and decomposition temperature is up to 340 ℃, and viscosity index 155 is very suitable for high performance lubricating oil.People such as Helena.wagner utilize several different methods with grease methyl esters collateralization, carry out transesterify with polyvalent alcohol then and also obtain good effect.People such as S.gryglewicz utilize lard and vegetables oil to experimentize, and they are at first with the grease esterification, carry out transesterify with polyvalent alcohol carry effect enrichment unsaturated fatty acids methyl esters by branch for lard after, and catalyzer is Ca (CH
3O)
2, productive rate reaches 85%～90% behind the reaction times 20h, finds that simultaneously the high more product low-temperature performance of degree of unsaturation is good more.Not not appearing in the newspapers of direct production PETO.
Utilize the reaction of the ester-interchange method synthesis for polyol ester of report to have shortcomings such as transformation efficiency is low, long reaction time, utilize ester-interchange method synthetic polyol ester to be mostly trimethylolpropane fatty acid ester simultaneously, utilize ester-interchange method synthesis of pentaerythritol oleic acid ester actually rare.The method temperature of reaction height of old little firm grade, time are long, the catalyzer cost is higher, are unfavorable for suitability for industrialized production; People's such as Zhou Cun method exists metal oxide and oleic acid to form the oleic acid salt, produces a certain amount of foam in reaction flask, brings difficulty to product separation, acid-alcohol ratio is 1: 3.6 simultaneously, make not complete reaction of tetramethylolmethane, the product hydroxyl value rises, and is unfavorable for the shortcomings such as use as lubricating oil; Traditional sulfuric acid catalysis rule exist reaction conversion ratio low, to shortcomings such as equipment corrosion are big.
The synthetic method that PETO is traditional is to adopt the vitriol oil, at high temperature carries out esterification and makes.Because sulfuric acid etching apparatus seriously, the waste liquid of generation influences environment, and the consumption of alkali refining in the augmenting response aftertreatment, thereby is necessary to seek new catalyzer and replaces sulfuric acid.Tosic acid itself has all advantages of the vitriol oil, and it is a kind of organic acid, the anaerobic voltinism, also than a little less than the vitriol oil, technology is simpler for carboniogenesis, during as this catalyst for reaction, have active high, not etching apparatus, pollute remarkable advantages such as little, be subjected to investigator's extensive attention.Yet, Catalyzed by p-Toluenesulfonic Acid synthesis of pentaerythritol oleic acid ester remains homogeneous reaction, so problems such as still having the catalyst recovery difficulty, can't reuse, the water damage ratio is more serious, therefore, be necessary it immobilized on suitable carriers, product and catalyst separating conveniently also can be reused, reduce water and pollute, reduce production cost.
Summary of the invention
The object of the invention provides a kind of method of activated carbon supported p-methyl benzenesulfonic acid catalytic preparation PETO, adopt the activated carbon supported p-methyl benzenesulfonic acid catalysis technique catalysis oleic acid and the esterification of tetramethylolmethane, and the factor of conditioned response productive rates such as the proportioning of dosage, lipid acid and the tetramethylolmethane of catalyzer, temperature, time carried out systematic research, to determine best synthesis route.
Technical scheme of the present invention: a kind of preparation method of PETO, adopting activated carbon supported p-methyl benzenesulfonic acid is catalyzer, with oleic acid and tetramethylolmethane is that raw material carries out esterification, obtain the PETO first product, carry out molecular distillation again and handle, obtain the PETO product;
(1) activated carbon supported p-methyl benzenesulfonic acid Preparation of catalysts: gac is activated 2h under 120 ℃ of conditions, take by weighing 10g after the cooling, be immersed in 60g concentration and be in the solution of tosic acid of 45%-65% and soak 42h, suction filtration, under 110 ℃ of conditions, dry 5h, obtain p-methyl benzenesulfonic acid-activated-carbon catalyst that 45%-65% carries the acid amount after the cooling, it is standby to put into dry still;
(2) esterification: with oleic acid and tetramethylolmethane is raw material, and the acid alcohol mol ratio is 4: 1-4.8: 1, and the dosage of catalyzer is the 0-4% of raw material total mass, and temperature of reaction is 120-160 ℃, and the reaction times is 0.5-3h, gets the PETO first product;
(3) molecular distillation is handled: the PETO first product carries out molecular distillation again to be handled, the molecular distillation condition be vacuum tightness less than 0.1Pa, temperature is 180 ℃ and obtains the PETO product.
The preparation method of described PETO, the gac of economy, wide material sources is suitable carriers of load tosic acid, with the pickling process is carrying method, and gac selects for use the tosic acid solution of 45% concentration to flood, and the catalytic activity of catalyzer is suitable before and after the load; The acid alcohol mol ratio is 4.16: 1, and the catalyzer dosage is 2.51% of a raw material total mass, and esterification reaction temperature is 160 ℃, and the reaction times is 2.71h.
Beneficial effect of the present invention: the present invention adopts activated carbon supported p-methyl benzenesulfonic acid catalysis of solid catalyst reaction first, it is outstanding to have catalytic performance, and catalyzer is easy to separate from product, can not cause acid water pollution, environmental pollution is little, is one of environment-friendly type catalyzer.
PETO has favorable environment protection, can prolong the work-ing life of machine, has security preferably, has renewable performance.It can be used for synthesizing aircraft oil, is used as automotive lubricant, air compressor machine oil and non-flame properties hydraulic pressure wet goods.That neopentyl polyol ester has is renewable, cleaning and safety three big advantages.The expert thinks that neopentyl polyol ester has tangible practical significance to China Agricultural Structure Adjustment, energy security and comprehensively treating ecological environment.
Utilize infrared spectroscopy and thermogravimetry to study the surface properties of supported catalyst, the result shows: the gac of economy, wide material sources is suitable carriers of load tosic acid, with the pickling process is carrying method, tosic acid strength of solution about 45% is proper, the catalytic activity of catalyzer is suitable before and after the load, and the catalyzer of 45% left and right sides charge capacity relatively is fit to the reaction of this class.Esterification is by the single factor experiment of temperature, time, catalyzer dosage and acid alcohol ratio, and catalyzer dosage, acid alcohol ratio and the test of the response surface in reaction times and the analysis of mountain range ridge, final definite reaction conditions is 160 ℃ of temperature, the catalyzer dosage is 2.51% of a raw materials quality, the acid alcohol mol ratio is 4.16: 1, and the reaction times is 2.71h, and the reaction esterification yield is greater than 95%, after handling, molecular distillation obtains the product of PETO, product yield about 80%.
Description of drawings
The charge capacity of Fig. 1 different carriers tosic acid
The concentration of Fig. 2 tosic acid solution is for the influence of charge capacity
Fig. 3 catalyzer carries the influence of acid amount to the reaction esterification yield
Fig. 4 gac, activated carbon supported catalyzer infrared spectrogram
The thermogravimetric curve of Fig. 5 gac, activated carbon supported catalyzer
The relation of Fig. 6 temperature and esterification yield
The relation of Fig. 7 catalyst levels and esterification yield
The relation of Fig. 8 material ratio and esterification yield
The esterification yield of Fig. 9 differential responses time
Figure 10 acid amount of carrying is the relation of number of times with the reaction esterification yield of 45% catalyst
Embodiment
Interaction between tosic acid and the carrier surface directly has influence on the firm degree and year what of acid amount of load, the esterification utilization be the acidity of catalyzer, thereby, the load of tosic acid and the acid-basicity of carrier surface are closely related, carrier surface alkalescence is too strong, acidity of catalyst is weakened greatly, even lose activity.The present invention has compared wide material sources, and cheap gac, diatomite, polynite and attapulgite are for the acid amount of carrying of tosic acid, and the result as shown in Figure 1.
On structure, gac, diatomite, attapulgite and polynite all are good carriers, but as shown in Figure 1, under identical condition, the acid amount of carrying of gac is far longer than other three kinds of carriers.The reason that this phenomenon occurs may be: one, and gac has more suitably surface tissue than other three kinds of carriers, and its specific surface area is bigger, and pore structure is abundanter; Two, the surface chemical property of gac is more suitable for the absorption of tosic acid.Gac is the suitable carrier of load tosic acid.
The concentration of embodiment 2 tosic acid solution is for the influence of carrying the acid amount
Take by weighing a certain amount of gac and under 120 ℃ of conditions, activate 2h, take by weighing 10g after the cooling and be immersed in the solution of tosic acid of 60g different concns (25%, 35%, 45%, 55%, 65%) and soak 42h, suction filtration.Dry 5h under 110 ℃ of conditions, obtain the different catalyzer that carry the acid amount after the cooling, it is standby to put into dry still.As shown in Figure 2, loading increases along with the increase of tosic acid strength of solution, after the tosic acid strength of solution reaches 45%, loading increases slowly, reason may be as follows: the tosic acid and the tosic acid in the solution of activated carbon surface absorption reach a dynamic balance, and loading no longer increases.
Embodiment 3 different influences of carrying the acid amount to reaction
The catalyzer of getting equivalent different loads amount reacts, reaction conditions is an oleic acid, tetramethylolmethane mol ratio 4: 1, catalyst consumption is 2% of a reactant total mass, 140 ℃ of reaction 2h, obtain catalyzer and carry the acid amount a series of data corresponding with the esterification yield of product, as shown in Figure 3, the content of the active ingredient in the catalyzer directly influences activity of such catalysts, and the activity of such catalysts component increases with the increase of carrying the acid amount, the growth that reaches esterification yield after 45% when year acid amount is just compared gently, the reason that this phenomenon occurs may be that loss of active component is bigger when year acid amount is excessive, and esterification yield increases slowly.Thereby select to carry acid amount about 45% and be advisable.
The comparison of catalyst activity before and after embodiment 4 loads
Get two parts of oleic acid, 4.4: 1 raw material of tetramethylolmethane mol ratio, adding the tosic acid of raw material total mass 0.9% and the loaded catalyst of raw material total mass 2% respectively reacts, 140 ℃ are reacted 2h, compare the catalytic activity of two kinds of catalyzer, result such as following table 1;
The comparison of the Phenylsulfonic acid catalytic activity after table 1 tosic acid and the load
| Catalyzed by p-Toluenesulfonic Acid esterification yield (%) | Loaded catalyst esterification yield (%) | |
| 1 | 96.25 | 95.44 |
| 2 | 96.01 | 95.12 |
| On average | 96.13 | 95.28 |
As shown in table 1, the catalytic activity of catalyzer before and after load changes little.The catalytic effect of load rear catalyst slightly descends before than load.The reason that this phenomenon occurs may be: gac is divided into monomolecular adsorption and two stages of multimolecular adsorption for the absorption of tosic acid.Be the unit molecule diffusion at first, the tosic acid molecular adsorption is on the surface of carrier, the concentration relationship of the size of this stage charge capacity and tosic acid solution is bigger, after monomolecular adsorption reaches capacity, the tosic acid molecule that continues to increase begins to be deposited on the molecule that has adsorbed, form polymolecular layer, and the bonding force between the polymolecular layer is less.Be adsorbed on its acid and heterogeneity of tosic acid of activated carbon surface, enter more firm that tosic acid on the strong adsorption site is adsorbed at first, acidity a little less than, and the esterification utilization is exactly the acidity of catalyzer, so, under catalyzer (loaded catalyst is converted into the catalytic amount of the load) katalysis of similar quality, the catalyzer esterification yield of loading type is lower.
During molecular vibration, must be attended by the variation of instanteneous dipole moment, a molecule has multiple mode of vibration, only makes molecular dipole apart from the mode of vibration that changes, and just can absorb the ir radiation of CF.This mode of vibration is called and has infrared active.When having only frequency when frequency and certain vibration of molecule of the ir radiation of irradiation molecule identical, behind the molecular absorption energy, transit to the vibrational level of higher-energy from the ground state vibrational level, thus on collection of illustrative plates the corresponding absorption band of appearance.Infrared spectra is that material is carried out one of means qualitatively.Reaching the standard grade among Fig. 4 is the infared spectrum of gac, rolls off the production line to be the infared spectrum of solid-carried catalyst.Because gac is as carrier, its transmittance is very low in infrared analysis, but still can see 1200cmu clearly from Fig. 4
-1SO in the peak tosic acid at place
2The flexible characteristic absorbance 1187.91cm of unsymmetrically
-1And 1120cm
-1SO
2The flexible characteristic absorbance 1039.90cm of symmetry
-1And 1009.43cm
-1, tosic acid has been described on the gac in the load.
Thermogravimetry (TGA) is under temperature programmed control, and a kind of technology of the quality of measurement of species and temperature variation is widely used in the immobilized research of catalyzer.Dotted line and solid line are represented the thermogravimetric curve of carrier activated carbon and load tosic acid respectively among Fig. 5.Two curves of actual situation in the comparison diagram 5 as seen, two curves all have apparent in view weightlessness in 0-120 ℃ scope, the reason that this phenomenon occurs may be the volatilization of combination water.Dotted line has kept constant later on substantially from 120 ℃, and solid line has weightlessness in 250-500 ℃ of scope, tangible weightlessness is particularly arranged about 300 ℃, this has illustrated on the gac after the load in the load really tosic acid, obvious weightlessness about 300 ℃ is due to the tosic acid decomposition.Simultaneously, it can also be seen that the catalyzer after immobilized has stronger stability in the temperature below 250 ℃, be suitable for the catalysis of such reaction by Fig. 5.
Embodiment 7 temperature are to the influence of reaction
Got oleic acid, tetramethylolmethane mol ratio 4: 1, catalyzer is 2% of a reactant total mass, reaction 2h, and constant pressure, the research temperature is to the influence of esterification yield, experimental result such as Fig. 6.
Esterification reaction temperature is crucial, as seen from Figure 6, and along with the rising of temperature, the activity of reactant increases, and speed of response is accelerated, thereby causes the continuous rising of esterification yield, but to the trend that rises 150 ℃ the time mild, 160 ℃ have only been improved 0.28% than 150 ℃, temperature of reaction fixes on 150-160 ℃.
Got oleic acid, tetramethylolmethane mol ratio 4: 1,160 ℃ of temperature of reaction, reaction 2h, the research catalyst levels is to the influence of esterification yield, constant pressure, experimental result such as Fig. 7.As seen from Figure 7, increase along with catalyst levels, transformation efficiency significantly increases, when the catalyst quality mark reaches 3%, increase the amount of catalyzer again, the transformation efficiency increasing degree diminishes, and 4% addition has only improved 1% transformation efficiency than 3% addition, darken when catalyst levels reaction product greater than 3% time simultaneously, quality product descends.The reason that this phenomenon occurs may be: the increase of catalyst levels, the active centre number that is provided increases, speed of response is accelerated, transformation efficiency has also been improved, but meanwhile resistance to mass transfer also can increase, when the catalyst quality mark is increased to a certain degree, because the influence of resistance to mass transfer can make speed of response can not increase again.Under this experiment condition, catalyst levels accounts for 2% of total reactant quality and is advisable.
The influence of embodiment 9 acid alcohols comparison reaction
By the oleic acid of design, the molar ratio of tetramethylolmethane, catalyst levels is former 2% of the total mass of trembling, 160 ℃ of temperature of reaction.Reaction times 2h, constant pressure, the research reaction times is to the influence of esterification yield, experimental result such as Fig. 8.As seen from Figure 8, according to chemical equilibrium theory, oleic increase can be carried out to the positive reaction direction by driving a reaction, and esterification yield is risen to some extent, but the trend that rises is not very big, by 1: 4.2 o'clock.It is the highest by 95.02% that esterification yield reaches.But oleic acid is excessive to be caused product residual when too many hyper acid, so that esterification yield descends, simultaneously oleic excessive, is unfavorable for the carrying out of aftertreatment.Thereby material ratio is chosen in about 1: 4.2.
10 reaction times of embodiment are to the influence of reaction
Got oleic acid, tetramethylolmethane mol ratio 4: 1,160 ℃ of temperature of reaction, 2% of catalyst reaction thing total mass, the research reaction times is to the influence of esterification yield, constant pressure, experimental result such as Fig. 9.As seen from Figure 9, in the last stage that reaction is carried out, As time goes on, esterification yield constantly rises, and 2.5h reaches maximum value, along with the continuation in reaction times is passed, esterification yield keeps constant and downtrending is arranged, and the reason that this situation occurs may be under water, catalyzer, hot conditions, and reaction is carried out to the reversed reaction direction, the ester hydrolysis of part goes out acid, makes reaction conversion ratio descend.So the reaction times is selected about 2.5h.
Take all factors into consideration esterification yield and cost, select material ratio 4.16: 1, catalyst levels 2.51%, time 2.7h and temperature are optimum process condition for 160 ℃, carry out confirmatory experiment reaction esterification yield with this understanding and reach 95.88%, meet the rule that the mountain range ridge is analyzed.
Utilize molecular distillation technique that thick product is carried out separation and purification, its main purpose is to remove oleic acid excessive in the raw material and unreacted half ester completely.Under the condition of 180 ℃ of service temperatures, pressure 0.1Pa, obtain the product of acid number less than 1mgKOH/g.The product yield is about 80%, compares with column chromatography, and not only velocity of separation improves, and yield also increases.
Embodiment 11 repeated experiments
Get oleic acid, 4.16: 1 raw material of tetramethylolmethane mol ratio, add to carry the acid amount respectively and be about 45% catalyzer 2.51% and react reaction times 2.71h, the multiplicity of checking catalyzer, result such as Figure 10.
Stability and the firm degree of absorption are the key issues of tosic acid load, also are the major issues that reduces production costs.Because absorption and desorb are reversible processes, the desorb of tosic acid is inevitable.Carry the acid amount when low, tosic acid hardly can solution-off, but charge capacity is low excessively, its esterification yield is very low, is unfavorable for industrialized production, along with the increase of carrying the acid amount, it is remarkable that desorption becomes, but along with the increase of charge capacity, along with the increase of reaction multiplicity, the reaction esterification yield is descending on the contrary, the reason that this situation occurs may be when year acid amount is excessive, tosic acid molecule on the polymolecular layer since bonding force a little less than, loss of active component is bigger, esterification yield descends very fast.After carrying the loaded catalyst reaction 5 times of acid amount about 45%, the reaction esterification yield is also about 85%, and as can be seen, the catalyzer after immobilized has stronger stability, is suitable for the catalysis of such reaction.
Claims (2)
1, a kind of preparation method of PETO, it is characterized in that adopting activated carbon supported p-methyl benzenesulfonic acid is catalyzer, is that raw material carries out esterification with oleic acid and tetramethylolmethane, obtains the PETO first product, carry out molecular distillation again and handle, obtain the PETO product;
(1) activated carbon supported p-methyl benzenesulfonic acid Preparation of catalysts: gac is activated 2h under 120 ℃ of conditions, take by weighing 10g after the cooling, be immersed in 60g concentration and be in the solution of tosic acid of 45%-65% and soak 42h, suction filtration, under 110 ℃ of conditions, dry 5h, obtain p-methyl benzenesulfonic acid-activated-carbon catalyst that 45%-65% carries the acid amount after the cooling, it is standby to put into dry still;
(2) esterification: with oleic acid and tetramethylolmethane is raw material, and the acid alcohol mol ratio is 4: 1-4.8: 1, and the dosage of catalyzer is the 0-4% of raw material total mass, and temperature of reaction is 120-160 ℃, and the reaction times is 0.5-3h, gets the PETO first product;
(3) molecular distillation is handled: the PETO first product carries out molecular distillation again to be handled, the molecular distillation condition be vacuum tightness less than 0.1Pa, temperature is 180 ℃ and obtains the PETO product.
2, the preparation method of PETO according to claim 1, the gac that it is characterized in that economy, wide material sources is the suitable carrier of load tosic acid, with the pickling process is carrying method, gac selects for use the tosic acid solution of 45% concentration to flood, and the catalytic activity of catalyzer is suitable before and after the load; The acid alcohol mol ratio is 4.16: 1, and the catalyzer dosage is 2.51% of a raw material total mass, and esterification reaction temperature is 160 ℃, and the reaction times is 2.71h.
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| CN105541612A (en) * | 2015-12-17 | 2016-05-04 | 南京科技职业学院 | Method for catalyzed synthesis of lubricating base oil from supported ionic liquid |
| CN110776443A (en) * | 2018-12-14 | 2020-02-11 | 瑞孚信江苏药业股份有限公司 | Preparation method of p-methylsulfonyl phenyl serine ethyl ester |
| CN110845331A (en) * | 2019-10-10 | 2020-02-28 | 天津利安隆新材料股份有限公司 | Preparation method of benzoic acid high-carbon alcohol ester |
| CN110746328A (en) * | 2019-10-12 | 2020-02-04 | 黄河三角洲京博化工研究院有限公司 | Method for removing odor of pentaerythritol tetra (3-mercaptopropionate) |
| CN115029165A (en) * | 2022-05-20 | 2022-09-09 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Methanol diesel oil micro-emulsification dispersant, preparation method and application thereof |
| CN115029165B (en) * | 2022-05-20 | 2023-06-30 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Methanol diesel oil microemulsified dispersant and preparation method and application thereof |
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