CN103449970A - Preparation method of neopentyl glycol - Google Patents
Preparation method of neopentyl glycol Download PDFInfo
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- CN103449970A CN103449970A CN2012101669254A CN201210166925A CN103449970A CN 103449970 A CN103449970 A CN 103449970A CN 2012101669254 A CN2012101669254 A CN 2012101669254A CN 201210166925 A CN201210166925 A CN 201210166925A CN 103449970 A CN103449970 A CN 103449970A
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Abstract
The invention provides a preparation method of neopentyl glycol, and belongs to the technical field of the preparation of alcohols. The preparation method includes the following steps: (1) regulating the pH value of a hydroxypivalaldehyde solution to 7.5-10; (2) obtaining a neopentyl glycol crude product by catalytic hydrogenation of hydroxypivalaldehyde treated by the step (1) under the effect of a hydrogenation catalyst at the temperature of 110-140 DEG C and with the pressure of 2.0-5.0 Mpa; and (3) purifying the neopentyl glycol crude product obtained in the step (2). The content of esters and other side products in the neopentyl glycol crude product prepared by the preparation method of the neopentylene glycol is extremely low, and the yield and purity of the neopentyl glycol are improved. In addition, a hydroxypivalaldehyde raw material system can be directly used for catalytic hydrogenation without any treatment, processes of aldol condensation and catalytic hydrogenation for preparation of the neopentyl glycol can be reduced, and the production efficiency can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of neopentyl glycol, be specifically related to a kind of method of utilizing the standby neopentyl glycol of hydroxy pivalin aldehyde Hydrogenation, belong to pure preparing technical field.
Background technology
Neopentyl glycol (be NPG, chemical name: 2，2-dimethyl-1，3-propanediol) be a kind of stable dibasic alcohol.Neopentyl glycol is as a kind of important fine chemical product, mainly for the production of unsaturated polyester, polyester powder coating, oil-free alkyd resin, polyurethane foam plastic, synthetic softening agent, tensio-active agent, insulating material, printing-ink, stopper, synthetic aircraft oil oil dope etc.
The preparation method of neopentyl glycol mainly comprises condensation hydrogenation method and discrimination method, and wherein, the research of the standby neopentyl glycol of condensation hydrogenation legal system starts from 20 century 70s.The step of the standby neopentyl glycol of condensation hydrogenation legal system mainly comprises: (1) formaldehyde and isobutyric aldehyde carry out condensation reaction and generate hydroxy pivalin aldehyde under the tertiary amine catalyst effect; (2) hydroxy pivalin aldehyde solution, under the effect of the metal catalysts such as copper or nickel, is 100 ~ 180 ℃ in temperature, under the condition that pressure is 1 ~ 10MPa, by hydrogenation reaction, prepares neopentyl glycol.In step (1), formaldehyde and isobutyric aldehyde carry out aldol reaction and generate hydroxy pivalin aldehyde under the tertiary amine catalyst effect, in condensation reaction, also can generate the organic acid by product, as hydroxy new pentane acid, formic acid, isopropylformic acid, a part in these organic acid by products can further be reacted and generate the organic acid salt by product with tertiary amine catalyst, can reduce like this alkalescence of hydroxy pivalin aldehyde material system, even can cause the hydroxy pivalin aldehyde material system to be acid.In step (2), product after step (1) condensation reaction obtains neopentyl glycol through shortening, and in condensation reaction, not yet complete with tertiary amine catalyst neutralization reaction organic acid by product can further react with neopentyl glycol, the final by product neopentyl glycol organic acid acetic that generates, the boiling point of such material and the boiling point of neopentyl glycol approach, and therefore are difficult to it is separated from neopentyl glycol.The generation of above-mentioned neopentyl glycol organic acid acetic by product can cause the purity of neopentyl glycol and productive rate to reduce.
Chinese patent literature CN101993351A discloses a kind of production technique of neopentyl glycol, specifically comprises the steps that (1) used active nickel catalyst under 60 ~ 80 ℃ and 1 ~ 5MPa, under the organic solvent existence, hydroxy pivalin aldehyde is carried out to hydrogenation; (2) hydrogenated products re-uses mineral alkali and carries out saponification, obtains the thick product of neopentyl glycol, and the thick product of the neopentyl glycol obtained is made with extra care, and obtains highly purified neopentyl glycol.Hydroxy pivalin aldehyde described in this preparation method is obtained through condensation reaction under the tertiary amine catalyst effect by formaldehyde and isobutyric aldehyde, after condensation reaction, does not adopt any further separating measure, reaction mixture is directly used in to hydrogenation reaction and prepares neopentyl glycol.Because described hydroxy pivalin aldehyde does not pass through separating-purifying, so contain any or multiple in organic acid by product, organic acid salt by product and tertiary amine catalyst in hydroxy pivalin aldehyde.The hydroxy pivalin aldehyde that contains above-mentioned organic acid by product, organic acid salt by product or tertiary amine catalyst, under the active nickel catalyst effect, carries out hydrogenation reaction under 60 ~ 80 ℃ and 1 ~ 5MPa condition, generates neopentyl glycol and neopentyl glycol organic acid acetic by product.In step (2), the product after hydrogenation reaction is carried out under the mineral alkali condition to the saponification processing, make neopentyl glycol organic acid acetic by product be hydrolyzed to neopentyl glycol and corresponding acid under alkaline condition.In above-mentioned technology, process the product of hydroxy pivalin aldehyde catalytic hydrogenation reaction by saponification, the neopentyl glycol organic acid acetic hydrolysis that it is contained generates corresponding acid and the neopentyl glycol generated is wished in reaction, and the part acid generated in hydrolysis reaction has consumed the raw material that can generate neopentyl glycol, so just reduced the productive rate of neopentyl glycol, and having reduced the purity of neopentyl glycol, also there is complex production process in above-mentioned preparation method in addition, the problem that production efficiency is low.
Summary of the invention
Technical problem to be solved by this invention is to process by saponification the Ester contained in hydroxy pivalin aldehyde shortening product in prior art, the productive rate and the purity drop that cause neopentyl glycol, and complex production process, and then provide a kind of production method of the simple neopentyl glycol of technique that the hydrogenolysis of the shortening of hydroxy pivalin aldehyde and by product Ester can be carried out simultaneously.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of neopentyl glycol, comprise the steps:
(1) regulating the hydroxy pivalin aldehyde pH is 7.5 ~ 10;
(2) hydroxy pivalin aldehyde after step (1) is processed, under the hydrogenation catalyst effect, is 110 ~ 140 ℃ in temperature, under the condition that pressure is 2.0 ~ 5.0Mpa, through shortening, obtains the thick product of neopentyl glycol;
(3) the thick product of described neopentyl glycol obtained in step (2) is purified.
Described hydrogenation catalyst is for take the copper lanthanum catalyst that copper, lanthanum is active ingredient.
Described copper lanthanum catalyst is composed of the following components: cupric oxide, lanthanum trioxide and silica containing carrier, and wherein, described cupric oxide content is 40-60wt%, and described lanthanum trioxide content is 2-5wt%, and described silica containing vector contg is 35-58wt%.
In described step (1), adjust the pH value of described hydroxy pivalin aldehyde solution with alkaline matter, described alkaline matter is mineral alkali or organic bases;
Wherein, described mineral alkali is alkali metal hydroxide or alkaline carbonate, and described organic bases is fatty amine.
Described alkali metal hydroxide be in KOH, NaOH any one or multiple; Described alkaline carbonate is K
2cO
3, Na
2cO
3in any one or multiple; Described fatty amine is one or more in methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine.
In described hydroxy pivalin aldehyde solution, hydroxy pivalin aldehyde content is 45 ~ 75wt%, and solvent is 23 ~ 52wt%, and surplus is impurity.
Described solvent is water or organic solvent, and described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, ether or methyl tertiary butyl ether.
Described impurity comprises one or more in methyl alcohol, formaldehyde, isobutyric aldehyde, hydroxypentanoic acid-DOPCP, formic acid DOPCP, isopropylformic acid DOPCP, organic amine and organic acid salt.
In described step (1), regulating described hydroxy pivalin aldehyde pH is 7.5 ~ 8.5.
By formaldehyde and isobutyric aldehyde, condensation under the tertiary amine catalyst effect prepares described hydroxy pivalin aldehyde.
The present invention compared with prior art has following advantage:
(1) preparation method of neopentyl glycol of the present invention, be 7.5 ~ 10 by the pH value of adjusting hydroxy pivalin aldehyde solution, and be 110 ~ 140 ℃ in temperature, under the condition that pressure is 2.0 ~ 5.0Mpa, through shortening, prepares neopentyl glycol.Under above-mentioned reaction conditions, the by product neopentyl glycol organic acid acetic that hydroxy pivalin aldehyde solution generates in the shortening process directly hydrogenolysis is that neopentyl glycol and organic acid are pure accordingly.The present invention adopts and in hydrogenation process, to make the direct hydrogenolysis of neopentyl glycol organic acid acetic by product replace in prior art after hydrogenation reaction, hydrogenation products is carried out to the saponification processing, can reduce the saponification treatment step in the neopentyl glycol preparation method so on the one hand, shortened process, on the other hand, in the neopentyl glycol organic acid acetic, neopentyl glycol hydroxy new pentane acid ester hydrogenolysis is neopentyl glycol, need to generate the significant loss of hydroxy new pentane acid while having avoided hydrolysis, has improved the yield of neopentyl glycol product; In addition, when hydrogenolysis is neopentyl glycol and the corresponding alcohol of organic acid, the boiling point of corresponding alcohol is lower than sour boiling point, for example the boiling point of methyl alcohol is that 64.8 ℃, the boiling point of formic acid are 100.8 ℃, so also be convenient to corresponding alcohol is separated from neopentyl glycol, reduce energy consumption while separating, and improve the purity of neopentyl glycol.
(2) in the preparation method of neopentyl glycol of the present invention, when described hydrogenation catalyst is selected the copper lanthanum catalyst, this hydrogenation catalyst can improve the selectivity of hydroxy pivalin aldehyde shortening, the hydrogenolysis of Ester had to good promoter action simultaneously, while having overcome the conventional hydrogenation catalyst of application, can only improve hydrogenation reaction, and can't make ester class hydrogenolysis there is the problem of best effect simultaneously.Especially select by cupric oxide, lanthanum trioxide and contain specific surface area at 80～300 m
2during copper lanthanum catalyst that the typing between/g or unformed silica supports form, due to the highly selective of hydrogenation and the synergy of ester class hydrogenolysis, in the thick product of neopentyl glycol that makes the preparation method of neopentyl glycol of the present invention prepare, the content of the by product such as ester class is extremely low, improved the purity of neopentyl glycol, after tested, when adopting described copper lanthanum catalyst, in the preparation neopentyl glycol, move continuously in 100h, mass yield in the hydroxy pivalin aldehyde neopentyl glycol can be up to 104.7%, after underpressure distillation, the gas phase purity of product neopentyl glycol can be up to 99.67%.
(3) in the preparation method of neopentyl glycol of the present invention, further the described hydroxy pivalin aldehyde pH of restriction is 7.5 ~ 8.5, under this pH value condition, hydrogenation catalyst has high selectivity, and can improve the effect of hydrogenation catalyst to the Ester hydrogenolysis, after tested, move continuously in 100h in the preparation neopentyl glycol, take the mass yield of hydroxy pivalin aldehyde neopentyl glycol as up to 104.2%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.53%.
(4) hydroxy pivalin aldehyde described in the preparation method of neopentyl glycol of the present invention can select the condensation under the tertiary amine catalyst effect by formaldehyde and isobutyric aldehyde to prepare, due to catalytic hydrogenation reaction and hydrogenolysis having occurred in the present invention simultaneously, so can directly being used for carrying out shortening without any processing, condensation product prepares neopentyl glycol, reduce the processing step of the standby neopentyl glycol of condensation hydrogenation legal system, improved production efficiency.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, but the present invention is not limited to this.
embodiment 1
(1) with the NaOH solution of 5wt% and the KOH solution adjustment hydroxy pivalin aldehyde pH of 10wt%, be 10.0, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 79wt%, and water is 20wt%, and surplus is impurity;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that nickel catalyzator is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 0.1h
-1, H
2gas space velocity be 300h
-1, in temperature, be 110 ℃, pressure is that under the 2.0Mpa condition, reaction prepares the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 180 ℃, obtain neopentyl glycol.
After tested, in the run duration of 100h, in hydroxy pivalin aldehyde, the mass yield of neopentyl glycol is 100.4%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.15%.
embodiment 2
(1) use the Na of 10wt%
2cO
3the K of solution and 5wt%
2cO
3it is 9.5 that solution is adjusted the hydroxy pivalin aldehyde pH, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 45wt%, water is 52wt%, and surplus is impurity, and wherein said impurity comprises methyl alcohol, isobutyric aldehyde, isopropylformic acid DOPCP, triethylamine and other material;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that copper catalyst is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 0.3h
-1, H
2gas space velocity be 300h
-1, in temperature, be 120 ℃, pressure is that under the 3.5Mpa condition, reaction prepares the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 190 ℃, obtain neopentyl glycol.
After tested, in the run duration of 100h, in hydroxy pivalin aldehyde, the mass yield of neopentyl glycol is 101.7%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.23%.
embodiment 3
(1) adjusting pH hydroxy pivalin aldehyde solution value with the KOH solution of 5wt% is 9.0, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 55wt%, methyl alcohol is 20wt%, ether is 20wt%, and surplus is impurity, and wherein said impurity comprises methyl alcohol, isobutyric aldehyde, hydroxypentanoic acid-DOPCP, isopropylformic acid DOPCP;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that copper catalyst is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 0.5h
-1, H
2gas space velocity be 300h
-1, in temperature, be 130 ℃, pressure is that under the 4.0Mpa condition, reaction prepares the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 200 ℃, obtain neopentyl glycol.
After tested, in the run duration of 100h, in hydroxy pivalin aldehyde, the mass yield of neopentyl glycol is 101.7%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.30%.
embodiment 4
(1) adjusting the hydroxy pivalin aldehyde pH with the methylamine solution of 20wt% is 7.5, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 60wt%, water is 34wt%, surplus is impurity, and wherein said impurity comprises hydroxypentanoic acid-DOPCP, isopropylformic acid DOPCP, formic acid DOPCP;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that nickel catalyzator is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 0.7h
-1, H
2gas space velocity be 300h
-1, in temperature, be 140 ℃, pressure is that under the 4.5Mpa condition, reaction obtains the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 180 ℃, obtain neopentyl glycol.
After tested, in the run duration of 100h, in hydroxy pivalin aldehyde, the mass yield of neopentyl glycol is 103.7%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.42%.
embodiment 5
(1) with the ethylamine solution of 10wt% and the Tri N-Propyl Amine solution adjustment hydroxy pivalin aldehyde pH of 10wt%, be 8.0, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 68wt%, butanols is 14wt%, propyl alcohol is 12wt%, and surplus is impurity, and wherein said impurity comprises methyl alcohol, formaldehyde, isobutyric aldehyde, hydroxypentanoic acid-DOPCP, formic acid DOPCP, isopropylformic acid DOPCP, organic acid salt;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that copper catalyst is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 1.0h
-1, H
2gas space velocity be 300h
-1, 115 ℃ of temperature, under pressure 3.8Mpa condition, reaction obtains the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 190 ℃, obtain neopentyl glycol.
After tested, in the run duration of 100h, in the mass yield 103.9% of hydroxy pivalin aldehyde neopentyl glycol, after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.47%.
embodiment 6
(1) regulating the hydroxy pivalin aldehyde pH with the methylamine solution of 30wt% is 8.5, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 75wt%, water is 23wt%, surplus is impurity, and wherein said impurity comprises methyl alcohol, formaldehyde, isobutyric aldehyde, formic acid DOPCP, isopropylformic acid DOPCP;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that copper catalyst is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 1.5h
-1, H
2gas space velocity be 300h
-1, in temperature, be 110 ℃, pressure is that under the 4.5Mpa condition, reaction obtains the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 200 ℃, obtain neopentyl glycol.
After tested, in the run duration of 100h, the mass yield of hydroxy pivalin aldehyde neopentyl glycol of take is 104.2%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.53%.
embodiment 7
(1) regulating the hydroxy pivalin aldehyde pH with the Isopropylamine solution of 5wt% is 8.3, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 68wt%, ethanol is 27wt%, surplus is impurity, and wherein said impurity comprises methyl alcohol, formaldehyde, isobutyric aldehyde, formic acid DOPCP, isopropylformic acid DOPCP;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that the copper lanthanum catalyst is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 1.2h
-1, H
2gas space velocity be 300h
-1, in temperature, be 110 ℃, pressure is that under the 4.5Mpa condition, reaction obtains the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 200 ℃, obtain neopentyl glycol.
In the present embodiment, described copper lanthanum catalyst is composed of the following components: cupric oxide, lanthanum trioxide and silica containing carrier, the content that the content that the content of described cupric oxide is 40wt%, described lanthanum trioxide is 2wt%, described silica containing carrier is 58wt%.
After tested, in the run duration of 100h, the mass yield of hydroxy pivalin aldehyde neopentyl glycol of take is 104.7%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.67%.
embodiment 8
(1) with the Isopropylamine solution of 10wt% and the methylamine solution adjusting hydroxy pivalin aldehyde pH of 5wt%, be 7.8, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 57wt%, methyl tertiary butyl ether is 34wt%, surplus is impurity, and wherein said impurity comprises methyl alcohol, formaldehyde, isobutyric aldehyde, formic acid DOPCP, isopropylformic acid DOPCP;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that the copper lanthanum catalyst is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 1.1h
-1, H
2gas space velocity be 300h
-1, in temperature, be 110 ℃, pressure is that under the 4.5Mpa condition, reaction obtains the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 200 ℃, obtain neopentyl glycol.
In the present embodiment, described copper lanthanum catalyst is composed of the following components: cupric oxide, lanthanum trioxide and silica containing carrier, the content that the content that the content of described cupric oxide is 50wt%, described lanthanum trioxide is 3wt%, described silica containing carrier is 47wt%.
After tested, in the run duration of 100h, the mass yield of hydroxy pivalin aldehyde neopentyl glycol of take is 103.7%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.42%.
embodiment 9
(1) regulating the hydroxy pivalin aldehyde pH with the Isopropylamine solution of 5wt% is 8.5, in described hydroxy pivalin aldehyde solution, by percentage to the quality, hydroxy pivalin aldehyde is 63wt%, methyl alcohol 31wt%, surplus is impurity, and wherein said impurity comprises methyl alcohol, formaldehyde, isobutyric aldehyde, formic acid DOPCP, isopropylformic acid DOPCP;
(2) adopt fixed-bed reactor as the catalytic hydrogenation reaction device, the hydroxy pivalin aldehyde solution after step (1) is processed is joined in the fixed-bed reactor that the copper lanthanum catalyst is housed, at H
2under existence, the liquid air speed of controlling hydroxy pivalin aldehyde solution is 1.3h
-1, H
2gas space velocity be 300h
-1, in temperature, be 110 ℃, pressure is that under the 4.5Mpa condition, reaction obtains the thick product of neopentyl glycol;
(3) be absolute pressure 0.02MPa by the thick product of neopentyl glycol obtained in step (2) at pressure, carry out the underpressure distillation purification under the condition that temperature is 200 ℃, obtain neopentyl glycol.
In the present embodiment, described copper lanthanum catalyst is composed of the following components: cupric oxide, lanthanum trioxide and silica containing carrier, the content that the content that the content of described cupric oxide is 60wt%, described lanthanum trioxide is 5wt%, described silica containing carrier is 35wt%.
After tested, in the run duration of 100h, the mass yield of hydroxy pivalin aldehyde neopentyl glycol of take is 103.9%, and after underpressure distillation, the gas phase purity of product neopentyl glycol is 99.61%.
In above-described embodiment, in described copper lanthanum catalyst, silica containing carrier can be selected any one in silica gel, white carbon black, silica zeolite or diatomite.
The copper catalyst used in above-described embodiment, nickel catalyzator, copper lanthanum catalyst and hydroxy pivalin aldehyde are the laboratory preparation, and the preparation method is as described below, and other raw material that uses is known, commercially available industrial chemicals.
The preparation method of described copper catalyst and described nickel catalyzator is as follows: take diatomite as carrier, silica containing carrier, cupric nitrate or nickelous nitrate are mixed with water, obtain mixing solutions, wherein the mol ratio of silica containing carrier, copper or nickel, water is 1:1:90, add 15% sodium carbonate solution in mixing solutions, under 80 ℃ of conditions, precipitate, controlling the precipitation endpoint pH is 10, will contain the aging 4h of solution of precipitation.By sedimentation and filtration, the 120 ℃ of oven dry that are deposited in to after filtering, after 400 ℃ of roastings, obtain described copper catalyst or described nickel catalyzator.
The preparation method of described copper lanthanum catalyst is as follows: (1) adds water by silica containing carrier, cupric nitrate and the lanthanum nitrate of specified quantitative and mixes under 40 ℃ of conditions; (2) in the mixed material of step (1), adding precipitation agent, the sodium carbonate solution that described precipitation agent is 10wt%, reaction under 90 ℃, the amount of the precipitation agent added by adjusting, controlling reaction end pH value is 10, then exists
80under ℃ aging 20 hours; (3) feed liquid after step (2) is processed is filtered, filter cake washing is by 120 ℃ of dryings after 30 hours, then, 650 ℃ of lower roastings 12 hours, obtains copper lanthanum catalyst product.
The preparation method of described hydroxy pivalin aldehyde is as follows: take isobutyric aldehyde and formaldehyde as raw material, three still series connection synthesis of hydroxy pivalyl aldehydes.It is 0.5MPa that first reactor is filled with to nitrogen to pressure, temperature is increased to 70 ℃, under agitation, formaldehyde, isobutyric aldehyde, Trimethylamine 99, triethylamine, water are joined in reactor, the mol ratio of wherein said formaldehyde, isobutyric aldehyde, Trimethylamine 99, triethylamine, water is (1.01 ~ 1.1): 1:(0.01 ~ 0.02): (0.007 ~ 0.009): (8 ~ 9), under agitation reacted 30 minutes.Material imports continuously in second reactor, under 70 ℃, the condition of 0.5MPa, is under agitation reacted 30 minutes.Material imports continuously in the 3rd reactor, under 70 ℃, the condition of 0.5MPa, under whipped state, reacts 30 minutes.Material imports receiving vessel continuously.The mixture that obtains is-0.07 in vacuum tightness ~-carry out underpressure distillation under 0.09MPa, the condition of 60 ~ 110 ℃, remove the light constituents such as isobutyric aldehyde, water, obtain hydroxy pivalin aldehyde.
Organic solvent (methyl alcohol, ethanol, propyl alcohol, butanols, ether, methyl tertiary butyl ether): Tianjin recovery fine chemistry industry institute, chemical pure;
Organic bases (methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine), Tianjin recovery fine chemistry industry institute, chemical pure;
Mineral alkali (KOH, NaOH, K
2cO
3, Na
2cO
3): Tianjin recovery fine chemistry industry institute, chemical pure.
Except the copper catalyst for the hydrogenation catalyst hydroxy pivalin aldehyde described in above-described embodiment, nickel catalyzator, copper lanthanum catalyst, the hydrogenation catalyst of the hydroxy pivalin aldehyde for the hydrogenation catalyst hydroxy pivalin aldehyde that the available technology adopting any means prepares all can be used for the present invention.
In addition, except the hydroxy pivalin aldehyde described in above-described embodiment, the hydroxy pivalin aldehyde that the available technology adopting any means prepares all can adopt neopentyl glycol preparation method of the present invention to prepare neopentyl glycol through shortening.
comparative Examples
Adopt fixed-bed reactor as the catalytic hydrogenation reaction device, hydroxy pivalin aldehyde solution is dropped in reactor, wherein, by percentage to the quality, in hydroxy pivalin aldehyde solution, hydroxy pivalin aldehyde is 75wt%, and methyl alcohol is 23wt%, in reactor, adds active nickel catalyst, under the hydrogen pressure of 3.5MPa, in 80 ℃ of reaction 2 ~ 3h, obtain hydrogenated products, described hydrogenated products is added to the sodium hydroxide solution of 5wt%, DOPCP class is wherein processed in saponification, obtains the thick product of neopentyl glycol; Be absolute pressure 0.02MPa to the thick product of the neopentyl glycol obtained at pressure, carry out the underpressure distillation purification under the condition that temperature is 200 ℃, obtain neopentyl glycol.
After tested, in the run duration of 100h altogether, in the mass yield 78.02% of hydroxy pivalin aldehyde neopentyl glycol, after underpressure distillation, the gas phase purity of product neopentyl glycol is 93.17%.
In above-mentioned Comparative Examples, the preparation method who provides in Chinese patent literature CN101993351A is provided the preparation method of neopentyl glycol.
The data that obtained from Comparative Examples, hydroxy pivalin aldehyde solution catalyzing hydrogenation prepares neopentyl glycol, and after then neopentyl glycol being carried out to saponification processing purification, the mass yield of the neopentyl glycol prepared is lower, be only 78.02%, after underpressure distillation, the gas phase purity of neopentyl glycol is only 93.17%.
Obviously, above-described embodiment is only for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments, and the apparent variation of being extended out thus or change are still among the protection domain in the invention claim.
Claims (10)
1. the preparation method of a neopentyl glycol, comprise the steps:
(1) regulating the hydroxy pivalin aldehyde pH is 7.5 ~ 10;
(2) hydroxy pivalin aldehyde after step (1) is processed, under the hydrogenation catalyst effect, is 110 ~ 140 ℃ in temperature, under the condition that pressure is 2.0 ~ 5.0Mpa, through shortening, obtains the thick product of neopentyl glycol;
(3) the thick product of described neopentyl glycol obtained in step (2) is purified.
2. the preparation method of neopentyl glycol according to claim 1, is characterized in that, described hydrogenation catalyst is for take the copper lanthanum catalyst that copper, lanthanum is active ingredient.
3. the preparation method of neopentyl glycol according to claim 2, it is characterized in that, described copper lanthanum catalyst is composed of the following components: cupric oxide, lanthanum trioxide and silica containing carrier, wherein, described cupric oxide content is 40-60wt%, described lanthanum trioxide content is 2-5wt%, and described silica containing vector contg is 35-58wt%.
4. according to the preparation method of the arbitrary described neopentyl glycol of claim 1 ~ 3, it is characterized in that, in described step (1), adjust the pH value of described hydroxy pivalin aldehyde solution with alkaline matter, described alkaline matter is mineral alkali or organic bases;
Wherein, described mineral alkali is alkali metal hydroxide or alkaline carbonate, and described organic bases is fatty amine.
5. the preparation method of neopentyl glycol according to claim 4, is characterized in that, described alkali metal hydroxide be in KOH, NaOH any one or multiple; Described alkaline carbonate is K
2cO
3, Na
2cO
3in any one or multiple; Described fatty amine is one or more in methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine.
6. according to the preparation method of the arbitrary described neopentyl glycol of claim 1 ~ 5, it is characterized in that, in described hydroxy pivalin aldehyde solution, hydroxy pivalin aldehyde content is 45 ~ 75wt%, and solvent is 23 ~ 52wt%, and surplus is impurity.
7. the preparation method of neopentyl glycol according to claim 6, is characterized in that, described solvent is water or organic solvent, and described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, ether or methyl tertiary butyl ether.
8. according to the preparation method of claim 6 or 7 described neopentyl glycol, it is characterized in that, described impurity comprises one or more in methyl alcohol, formaldehyde, isobutyric aldehyde, hydroxypentanoic acid-DOPCP, formic acid DOPCP, isopropylformic acid DOPCP, organic amine and organic acid salt.
9. according to the preparation method of the arbitrary described neopentyl glycol of claim 1 ~ 8, it is characterized in that, in described step (1), regulating described hydroxy pivalin aldehyde pH is 7.5 ~ 8.5.
10. according to the preparation method of the arbitrary described neopentyl glycol of claim 1 ~ 9, it is characterized in that, by formaldehyde and isobutyric aldehyde, condensation under the tertiary amine catalyst effect prepares described hydroxy pivalin aldehyde.
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