CN107540521A - The method of hydroxy pivalin aldehyde Hydrogenation neopentyl glycol - Google Patents
The method of hydroxy pivalin aldehyde Hydrogenation neopentyl glycol Download PDFInfo
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- CN107540521A CN107540521A CN201610495197.XA CN201610495197A CN107540521A CN 107540521 A CN107540521 A CN 107540521A CN 201610495197 A CN201610495197 A CN 201610495197A CN 107540521 A CN107540521 A CN 107540521A
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- hydroxy pivalin
- pivalin aldehyde
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Abstract
The present invention provides a kind of method of hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol, mainly solves the problems, such as that impurity ester conversion rate is low in existing raw material.The present invention uses following steps：(1) hydroxy pivalin aldehyde raw material is hydrogenated with 100~180 DEG C and 1.5~4MPa of pressure using copper-aluminium catalyst；(2) the impurity ester in the hydrogenated products of step 1 is hydrogenated with 200~250 DEG C and 3~5MPa of pressure using copper Si catalyst；(3) product obtained to step 2 refines, and obtains the neopentyl glycol of high-purity.The technical scheme of the two-stage hydrogenation preferably solves above mentioned problem, the industrialized production available for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol.
Description
Technical field
The present invention relates to a kind of method of hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol.
Background technology
Neopentyl glycol (NPG) is a kind of important intermediate, has the dihydric alcohol of typical neopentyl structure, is mainly used in giving birth to
Produce polyester resin, PEPA and synthetic lubricant fluid esters, polymeric plasticizer and alkyd resin etc..Using neopentyl glycol as
The polyester powder coating of raw material production has excellent mobility, pliability, chemical stability, resistance to because neopentyl structure be present
The performances such as Hou Xing, chlorine resistance, heat endurance and UV resistant irradiation.With the enhancing of people's energy conservation and environmental awareness, powdery paints,
The environmental protection coating material rapid developments such as the solid component coating of height, have driven the rapid growth to neopentyl glycol demand.
The industrialized production route of neopentyl glycol mainly has halo propyl alcohol route and isobutylaldehyde route.Halo propyl alcohol route with
2,2- dimethyl -3- chloros propyl alcohol are initiation material, are first etherified, then alkaline hydrolysis generation neopentyl glycol, because raw material is in short supply, yield pole
It is micro-.Industrial production neopentyl glycol uses isobutylaldehyde route both at home and abroad at present, i.e., using isobutylaldehyde, formaldehyde as initiation material, through alkali
Property catalyst is condensed into intermediate 2, and 2- pentaldols are commonly called as hydroxy pivalin aldehyde, and abbreviation HPA, HPA are by formaldehyde discrimination
Change or catalytic hydrogenating reduction is neopentyl glycol, discrimination method and hydrogenation method are referred to as again in technique.External production new penta 2 at present
The technique of alcohol generally uses condensation hydrogenation method, and the technique includes three units：Aldol condensation, catalytic hydrogenation and product purification.Should
Technique has the advantages such as environment-friendly, product quality is high.Traditional condensation discrimination method technique falls behind relatively, from product quality, warp
Index of helping all can not be compared with condensation hydrogenation method technique to environmental requirement.
Hydroxy pivalin aldehyde is generally condensed to yield by isobutylaldehyde and formaldehyde in organic amine catalyst.But unavoidably exist secondary
Reaction, such as isobutylaldehyde self-condensation react into ester, and hydroxy pivalin aldehyde self-condensation is into hydroxypivalyl hydroxypivalate neopentyl alcohol monoesters
(1115 ester), hydroxy pivalin aldehyde and formaldehyde generation neopentyl glycol etc..Using removal accessory substance and catalyst purification in existing process
To HPA therein, then it is hydrogenated with again, although reducing the poisoning possibility of hydrogenation catalyst, substantially increases energy consumption
With add cost.
It is poor to be typically due to HPA heat resistance, while hydrogenation reaction is carried out more than 160 DEG C, HPA points will be occurred
Solution, and formaldehyde caused by decomposing can cause hydrogenation catalyst to inactivate.Therefore, it should be hydrogenated with as far as possible in lower temperature.It is another
Aspect, the hydrogenation of impurity ester usually require higher temperature, and hydro-conversion of being tried one's best to the impurity ester in HPA solution is complete, otherwise
NPG product purities can be influenceed.
In United States Patent (USP) US4250337 embodiments 2, CuO (33wt%)-CrO is employed3-BaO/SiO2Hydrogenation catalyst,
At 145 DEG C, NPG selectivity and conversion ratio is preferable, but when Ba is as activity of hydrocatalyst element, catalyst life
It is short.In United States Patent (USP) US6201159 embodiments 2, the Raney's nickel catalyst of use does not observe that obvious inactivation is existing in 80 hours
As, but catalyst to the conversion ratio of impurity ester (neopentyl glycol monoesters) than relatively low.
U.S. EASTMAN employs HPA condensation liquids and directly carries out hydrogenation technique, therefore hydrogenation catalyst is proposed higher
Challenge.In United States Patent (USP) US4855515, cupric oxide/copper chromite catalyst for being promoted using manganese oxide, but its catalytic activity
Lower slightly, hydrogenation needs to carry out under conditions of 160~170 DEG C, however, raw material HPA solution is easily decomposed at this temperature, causes
Make to reduce NPG yields.Because catalyst uses chromium, environment is polluted.
The content of the invention
The technical problems to be solved by the invention are the problem of impurity ester conversion rate are low in existing HPA raw materials, there is provided a kind of
The method of hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol.This method can improve impurity on the premise of high HPA conversion ratios are obtained
Ester conversion rate and NPG yields, compared with conventional method, preparing neopentyl glycol with the method for the present invention, there is higher impurity ester to turn
The advantages of rate, accessory substance is few, and neopentyl glycol yield is high.
In order to solve the above-mentioned technical problem, the technical scheme of use is as follows：A kind of hydroxy pivalin aldehyde catalytic hydrogenation system new penta
The method of glycol, comprises the following steps：
(1) using copper-aluminium catalyst under conditions of 80~180 DEG C of reaction temperature, 1.5~4MPa of reaction pressure, to hydroxyl
Neovaleraldehyde raw material is hydrogenated with；
(2) using copper Si catalyst under conditions of 200~250 DEG C of reaction temperature, 3~5MPa of reaction pressure, to step
(1) the impurity ester in hydrogenated products is hydrogenated with；
(3) product obtained to step (2) refines, and obtains the neopentyl glycol of high-purity.
In above-mentioned technical proposal, it is preferred that the reaction temperature of step (1) is 120~160 DEG C
In above-mentioned technical proposal, it is preferred that copper-aluminium catalyst described in step (1) prepared by coprecipitation and by nickel,
Zinc, rhenium are modified to obtain.
In above-mentioned technical proposal, it is preferred that the copper content in copper-aluminium catalyst described in step (1) is 25~45wt%,
Aluminium content is 20~35wt%, and remaining is modifying agent.It is furthermore preferred that the copper content in copper-aluminium catalyst described in step (1) is
30~40wt%.
In above-mentioned technical proposal, it is preferred that the hydroxy pivalin aldehyde raw material described in step (1) is contracted by isobutylaldehyde and formaldehyde aldol
Close what is obtained.
In above-mentioned technical proposal, the copper-aluminium catalyst described in step (1) is prepared by coprecipitation, and co-precipitation temperature is without spy
Do not limit, but precipitation temperature is lower, advantageously forms little crystal grain.As for precipitating reagent, those skilled in the art can flexibly slap
Hold, such as, but not limited at least one of sodium carbonate, sodium acid carbonate, sodium hydroxide.
In above-mentioned technical proposal, the active specy of the copper Si catalyst described in step (2) is copper, its precursor salt prioritizing selection
At least one of copper nitrate, copper acetate, cupric oxalate.
In above-mentioned technical proposal, the copper Si catalyst described in step (2) is modified to obtain by zinc, chromium, manganese.
In above-mentioned technical proposal, the copper content in copper Si catalyst described in step (2) is 15~30wt%, and silicone content is
30~50wt%, remaining is modifying agent.
In above-mentioned technical proposal, the impurity ester described in step (2) is to be contracted by isobutylaldehyde and formaldehyde under Triethylamine catalyst
Close obtained accessory substance hydroxypivalyl hydroxypivalate neopentyl alcohol monoesters.
In above-mentioned technical proposal, the content of the impurity ester described in step (2) is 1~5wt%.
In above-mentioned technical proposal, the copper Si catalyst described in copper-aluminium catalyst and step (2) described in step (1) is using
Preceding carry out hydrogen reducing, reduction temperature are 300~400 DEG C, and the recovery time is 6~18 hours.
In above-mentioned technical proposal, the process for purification described in step (3) uses thin film evaporator rectifying.
The performance of catalyst is calculated as follows method evaluation：
C：HPA conversion ratios
S：NPG selectivity
Y：NPG yields
m1：HPA mass content in raw material
m1’：HPA mass content in product
m2：NPG mass content in raw material
m2’：NPG mass content in product
M1：HPA molal weights
M2：NPG molal weights
Hydroxy pivalin aldehyde hydrogenation activity appreciation condition：
Catalyst is carried out on pressurization static bed reaction unit, and the loadings of copper-aluminium catalyst are 20mL；Copper Si catalyst
Loadings 20mL.
Catalyst needs to carry out pre-reduction treatment before activity rating, and prereduction condition is：Containing H210% H2-N2It is mixed
Close in atmosphere, 350 DEG C of reduction temperatures 12 hours.
Appreciation condition：Liquid air speed 0.5h-1, gas space velocity 800h-1, reaction pressure 3MPa, the entrance temperature of copper-aluminium catalyst
130 DEG C of degree, 220 DEG C of the inlet temperature of copper Si catalyst.
Raw material composition HPA solution is obtained by isobutylaldehyde and formaldehyde under Triethylamine catalyst, HPA contents 60%, 1115 esters
Content 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with relatively low temperature using active copper-aluminium catalyst, suppresses HPA and decomposes, while and then use copper
Si catalyst realizes high 1115 ester conversion rate, greatly improves NPG total recoverys to the two-stage hydrogenation method of impurity ester through hydrogenation.
The method of the present invention is in above-mentioned appreciation condition, HPA conversion ratios 100%, and NPG is selectively more than 99%, 1115 esters
Conversion ratio is more than 90%, and HPA conversion ratios and selectivity are higher in existing method, but 1115 ester conversion rates are less than 60%, take
Obtained preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 110 DEG C and 3Mpa reactions, and product is by cooling down
Device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG crude products.
Impurity ester through hydrogenation：The NPG crude products of acquisition are squeezed into after reaction system mixes with the H2 after deoxidation by measuring pump and entered
Reactor.Copper Si catalyst 20ml is loaded in fixed bed reactors, 1115 esters generate NPG with hydrogen in 200 DEG C and 3Mpa reactions,
Product is cooled down by cooler, after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Embodiment 2】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 120 DEG C and 3.5Mpa reactions, and product is by cold
But device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG crude products.
Impurity ester through hydrogenation：The NPG crude products of acquisition are squeezed into reaction system and the H after deoxidation by measuring pump2Enter after mixing
Reactor.Copper Si catalyst 20ml is loaded in fixed bed reactors, 1115 esters generate NPG with hydrogen in 210 DEG C and 3Mpa reactions,
Product is cooled down by cooler, after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Embodiment 3】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 130 DEG C and 3.5Mpa reactions, and product is by cold
But device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG crude products.
Impurity ester through hydrogenation：The NPG crude products of acquisition are squeezed into after reaction system mixes with the H2 after deoxidation by measuring pump and entered
Reactor.Copper Si catalyst 20ml is loaded in fixed bed reactors, 1115 esters generate NPG with hydrogen in 220 DEG C and 3Mpa reactions,
Product is cooled down by cooler, after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Embodiment 4】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 140 DEG C and 4Mpa reactions, and product is by cooling down
Device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG crude products.
Impurity ester through hydrogenation：The NPG crude products of acquisition are squeezed into after reaction system mixes with the H2 after deoxidation by measuring pump and entered
Reactor.Copper Si catalyst 20ml is loaded in fixed bed reactors, 1115 esters generate NPG with hydrogen in 230 DEG C and 4Mpa reactions,
Product is cooled down by cooler, after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Embodiment 5】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 150 DEG C and 4Mpa reactions, and product is by cooling down
Device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG crude products.
Impurity ester through hydrogenation：The NPG crude products of acquisition are squeezed into after reaction system mixes with the H2 after deoxidation by measuring pump and entered
Reactor.Copper Si catalyst 20ml is loaded in fixed bed reactors, 1115 esters generate NPG with hydrogen in 240 DEG C and 4Mpa reactions,
Product is cooled down by cooler, after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Embodiment 6】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 140 DEG C and 4Mpa reactions, and product is by cooling down
Device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG crude products.
Impurity ester through hydrogenation：The NPG crude products of acquisition are squeezed into after reaction system mixes with the H2 after deoxidation by measuring pump and entered
Reactor.Copper Si catalyst 20ml is loaded in fixed bed reactors, 1115 esters generate NPG with hydrogen in 250 DEG C and 4Mpa reactions,
Product is cooled down by cooler, after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Comparative example 1】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 140 DEG C and 4Mpa reactions, and product is by cooling down
Device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Comparative example 2】
It is prepared by hydroxy pivalin aldehyde (HPA) raw material：It is about 1 in molar ratio by formalin and isopropanol：0.729 is matched somebody with somebody
Material, it is well mixed to obtain reaction solution A；It is about 0.9 in molar ratio by isobutylaldehyde and triethylamine：0.06 carries out dispensing, is well mixed
Obtain reaction solution B；Rectifying column is normal pressure, when tower top temperature reaches 80 DEG C, starts charging reaction, to tower top, tower reactor Produced Liquid
After carrying out gas chromatographic analysis, the content of isobutylaldehyde is 84.6wt% in overhead distillate, and triethylamine content is 8.4wt%, first
Alcohol content is 5.5wt%, isopropanol content 1.5wt%.The concentrated obtained hydroxy pivalin aldehyde raw material of tower reactor Produced Liquid is stand-by, its
HPA contents 60%, 1115 ester contents 5%, isobutyraldehyde content 1.5%, remaining is water.
HPA is hydrogenated with：HPA solution is direct plungeed into head tank without further processing, hydrogen by pressure regulator level pressure,
Through degasifier deoxidation, HPA solution squeezes into reaction system and the H after deoxidation by measuring pump after metering2Enter reactor after mixing.
Copper-aluminium catalyst 20ml is loaded in fixed bed reactors, aldehyde generates NPG with hydrogen in 210 DEG C and 4Mpa reactions, and product is by cooling down
Device cools down, and after gas-liquid separator carries out gas-liquid separation, obtains NPG products.
Raw material composition, HPA hydrogenated products composition, impurity ester through hydrogenation product form and HPA conversion ratios, NPG selectivity and
1115 ester conversion rates the results are shown in Table 1.
【Embodiment 7】
The NPG of embodiment 1~6 and comparative example 1~2 is refined by thin film evaporator, product form the results are shown in Table
2。
Table 1
Table 2
Claims (10)
1. a kind of method of hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol, comprises the following steps：
(1) it is new to hydroxyl using copper-aluminium catalyst under conditions of 100~180 DEG C of reaction temperature, 1.5~4MPa of reaction pressure
Valeral raw material is hydrogenated with；
(2) using copper Si catalyst under conditions of 200~250 DEG C of reaction temperature, 3~5MPa of reaction pressure, to step (1)
Impurity ester in hydrogenated products is hydrogenated with；
(3) product obtained to step (2) refines, and obtains the neopentyl glycol of high-purity.
2. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(1) copper-aluminium catalyst described in is prepared by coprecipitation and is modified to obtain by nickel, zinc, rhenium.
3. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(1) copper content in copper-aluminium catalyst described in is 25~45wt%, and aluminium content is 20~35wt%, and remaining is modifying agent.
4. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(1) what the hydroxy pivalin aldehyde raw material described in was obtained by isobutylaldehyde and formaldehyde aldol condensation.
5. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(2) the copper Si catalyst described in is modified to obtain by zinc, chromium, manganese.
6. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(2) copper content in copper Si catalyst described in is 15~30wt%, and silicone content is 30~50wt%, and remaining is modifying agent.
7. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(2) the impurity ester described in is the accessory substance hydroxypivalyl hydroxypivalate neopentyl alcohol monoesters obtained by isobutylaldehyde and formaldehyde condensation.
8. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(2) content of the impurity ester described in is 1~5wt%.
9. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(1) the copper Si catalyst described in copper-aluminium catalyst and step (2) described in carries out hydrogen reducing before use.
10. the method for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol according to claim 1, it is characterised in that：Step
(3) process for purification described in uses thin film evaporator or rectification under vacuum.
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| CN108623437A (en) * | 2018-06-01 | 2018-10-09 | 利华益集团股份有限公司 | A kind of method of continuous production neopentyl glycol |
| CN113121308A (en) * | 2021-04-21 | 2021-07-16 | 云南恒罡科技有限公司 | Method for synthesizing neopentyl glycol by catalytic hydrogenation of hydroxypentanal |
| CN113200816A (en) * | 2021-05-15 | 2021-08-03 | 公主岭市恒昌科技有限公司 | Hydroxypivalaldehyde hydrogenation process |
| CN115819185A (en) * | 2022-12-28 | 2023-03-21 | 南京大学扬州化学化工研究院 | Method for synthesizing neopentyl glycol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108623437A (en) * | 2018-06-01 | 2018-10-09 | 利华益集团股份有限公司 | A kind of method of continuous production neopentyl glycol |
| CN108623437B (en) * | 2018-06-01 | 2021-07-27 | 利华益集团股份有限公司 | Method for continuously producing neopentyl glycol |
| CN113121308A (en) * | 2021-04-21 | 2021-07-16 | 云南恒罡科技有限公司 | Method for synthesizing neopentyl glycol by catalytic hydrogenation of hydroxypentanal |
| CN113200816A (en) * | 2021-05-15 | 2021-08-03 | 公主岭市恒昌科技有限公司 | Hydroxypivalaldehyde hydrogenation process |
| CN116178105A (en) * | 2022-12-08 | 2023-05-30 | 万华化学集团股份有限公司 | Method for improving neopentyl glycol yield by catalytic decomposition of quaternary congenital ester |
| CN115819185A (en) * | 2022-12-28 | 2023-03-21 | 南京大学扬州化学化工研究院 | Method for synthesizing neopentyl glycol |
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