CN109232177A - A kind of method that catalytic hydrogenation prepares neopentyl glycol - Google Patents
A kind of method that catalytic hydrogenation prepares neopentyl glycol Download PDFInfo
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- CN109232177A CN109232177A CN201811240820.2A CN201811240820A CN109232177A CN 109232177 A CN109232177 A CN 109232177A CN 201811240820 A CN201811240820 A CN 201811240820A CN 109232177 A CN109232177 A CN 109232177A
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- neopentyl glycol
- catalytic hydrogenation
- nickel phosphide
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- hydroxy pivalin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a kind of methods that catalytic hydrogenation prepares neopentyl glycol, by hydroxy pivalin aldehyde under the catalytic action of nano nickel phosphide, add hydrogen that neopentyl glycol is made.A kind of method that catalytic hydrogenation prepares neopentyl glycol of the present invention, using nano nickel phosphide as hydrogenation catalyst, with very high activity and stability, nano nickel phosphide will not reunite in catalytic process, thermal stability is good, hardness is big, anti-oxidant and corrosion resistance is strong, higher surface-active bit density is shown, hydrogen-consuming volume is few, reusable；Nano nickel phosphide has the catalytic hydrogenation ability to compare favourably with noble metal, and can be used to continuous fixed bed reaction again and can be used for the still reaction of interval；Under more mild reaction condition, nickel phosphide can efficient catalytic hydroxy pivalin aldehyde add hydrogen to prepare neopentyl glycol；The catalyst system product postprocessing is simple, low in cost, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of methods that catalytic hydrogenation prepares neopentyl glycol, belong to the preparation field of polyalcohol.
Background technique
Neopentyl glycol (abbreviation NPG) molecule contains specific neopentyl structure and dihydric alcohol structure, makes it in polyester tree
The fields such as rouge, polyurethane, powdery paints and synthetic lubricant fluid are widely used, and assign these materials good thermal stability
And chemical stability.
The a large amount of high-purity neopentyl glycols of state's domestic demand at present, market has openings is larger, still there is a large amount of imports.Traditional production is new
The sodium formate method of pentanediol need to consume a large amount of formaldehyde, and byproduct sodium formate.Since sodium formate separates difficulty with neopentyl glycol, and
Sodium formate is the promotor that neopentyl glycol decomposes, and can seriously affect the quality of product, byproduct sodium formate removing is difficult, product quality
Difference, at high cost, economic benefit does not protrude.Hydrogenation method prepares neopentyl glycol purification simple process, and equipment is few, with low investment, at
This is low, is suitble to large-scale continuous production.Isobutylaldehyde and formaldehyde condensation have been generallyd use in the world is made hydroxy pivalin aldehyde, then plus
Hydrogen produces neopentyl glycol at the synthesis hydrogenation technique of neopentyl glycol.The key technology of condensation hydrogenation method is hydrogenation catalyst
Exploitation.Currently used hydrogenation catalyst includes precious metals pd, non-noble metal Ni system and Cu system.Noble metal valuableness is not suitable for big
Large-scale production；Nickel catalyst is using Raney's nickel or with Mo, Co etc. modified catalyst as representative, complicated components, and stability is poor, easy
To reunite, can inactivate quickly, service life is short, and it is at high cost, and prepare and post-process all more complicated；Cu-series catalyst is used for aldehyde
Class hydrogenation activity is poor, still needs to further modification, and the cost is relatively high.
Summary of the invention
Neopentyl glycol, which is prepared, in order to solve sodium formate method in the prior art need to consume a large amount of formaldehyde, and byproduct sodium formate, produce
Quality is poor, at high cost, economic benefit is not prominent and hydrogenation method to prepare hydrogenation catalyst research in neopentyl glycol not mature enough
A series of problems, such as, a kind of method that catalytic hydrogenation prepares neopentyl glycol is provided.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows:
A kind of method that catalytic hydrogenation prepares neopentyl glycol, by hydroxy pivalin aldehyde under the catalytic action of nano nickel phosphide,
Add hydrogen that neopentyl glycol is made.
In the prior art, since nano nickel phosphide surface can be larger, it is easy to reunite, synthesis is relatively difficult, therefore
Carrier is mostly used to disperse nickel phosphide.But for support type nickel phosphide, reactant has to pass through the interior diffusion in carrier duct
It can be contacted with activated centre.For hydroxy pivalin aldehyde molecule, because it contains compared with highly branched chain, its interior expansion in duct will affect
It dissipates, to reduce its reaction rate.Applicants have found that under cetyl trimethylammonium bromide protection, and use low temperature
Normal pressure dynamic solvent thermal method can synthesize stable nano nickel phosphide.And it is close that the nickel phosphide possesses higher Adsorption
Degree.
In order to further increase catalytic activity, the partial size of nano nickel phosphide is 30-60nm.
The method that above-mentioned catalytic hydrogenation prepares neopentyl glycol can not only use continuous fixed bed reaction, but also can use
The still reaction of interval.
When using continuous fixed bed reaction, specific preparation method is preferably as follows: nano nickel phosphide is loaded on fixation
In bed reactor, and the H at 200 ± 10 DEG C22 ± 0.1h is pre-processed in stream, then passes to the hydroxyl that mass concentration is 11 ± 2%
Neovaleraldehyde ethanol solution reacts under conditions of temperature is 80-130 DEG C, pressure is 0.5-3MPa, and neopentyl glycol is made.
In order to further ensure the conversion ratio of raw material and the selectivity of product, H2Molar ratio with hydroxy pivalin aldehyde is 5-
20；Hydroxy pivalin aldehyde liquid hourly space velocity (LHSV) is 0.5-2.0h-1。
Product uses gas chromatographic analysis.
When using batch tank reaction, specific preparation method is preferably as follows: the hydroxyl for being 11 ± 2% by mass concentration
Neovaleraldehyde ethanol solution is packed into autoclave together with nickel phosphide, successively uses He and H2Replacement reaction kettle, and be in temperature
100-150℃、H2Pressure reacts 2-5h under conditions of being 0.5-0.8MPa, is centrifuged off catalyst to get neopentyl glycol.
Above-mentioned reaction is to which after reaction, solid catalyst is using supercentrifuge separation, and product is using gas-chromatography point
Analysis.
In order to guarantee catalytic effect, the mass ratio of nano nickel phosphide and hydroxy pivalin aldehyde is 1:(110-200).
In order to guarantee catalytic activity, above-mentioned nano nickel phosphide follows these steps to synthesize: by nickel chloride, sodium dihydric hypophosphite and
Cetyl trimethylammonium bromide is dissolved in ethylene glycol solution, and will carry out hot place under mixture in oil bath return stirring state
Reason, then washs product, vacuum drying is to get nano nickel phosphide.
Further preferably, the molar ratio of nickel chloride and sodium dihydric hypophosphite is 1:(2-5), nickel chloride and cetyl front three
The molar ratio of base ammonium bromide is 1:(1-3).
Further preferably, the temperature of oil bath heat treatment is 150-170 DEG C, time 2-5h.
In order to improve the purity of catalyst, guarantee that catalytic effect, washing methods are to be taken out using alcohol-water mixed solution
Mention 24-36h, wherein the volume ratio of second alcohol and water is 1:(1-2).
The unmentioned technology of the present invention is referring to the prior art.
A kind of method that catalytic hydrogenation prepares neopentyl glycol of the present invention has very using nano nickel phosphide as hydrogenation catalyst
High activity and stability, nano nickel phosphide will not reunite in catalytic process, and thermal stability is good, hardness is big, anti-oxidant and resistance to
Corrosivity is strong, shows higher surface-active bit density, hydrogen-consuming volume is few, reusable；Nano nickel phosphide has and your gold
The catalytic hydrogenation ability that symbolic animal of the birth year matches in excellence or beauty, and can be used to continuous fixed bed reaction and can be used for the still reaction of interval；?
Under more mild reaction condition, nickel phosphide can efficient catalytic hydroxy pivalin aldehyde add hydrogen to prepare neopentyl glycol；The catalyst system produces
Object post-processing is simple, low in cost, it is easy to accomplish industrialized production.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
The preparation of nano nickel phosphide:
Nickel chloride, sodium dihydric hypophosphite and cetyl trimethylammonium bromide that molar ratio is 1:3:2 are dissolved in ethylene glycol
In solution, and mixture is heat-treated 3h under return stirring state in the oil bath that temperature is 155-165 DEG C, after reaction,
Solid product is extracted into 30h with the alcohol-water mixed solution that volume ratio is 1:1.5, vacuum drying is 30-60nm to get partial size
Nano nickel phosphide.
Embodiment 2
The nickel phosphide that 0.5g partial size is 30-60nm is loaded in fixed bed reactors, and the H at 200 DEG C2Locate in advance in stream
2h is managed, the hydroxy pivalin aldehyde ethanol solution that mass concentration is 11%, setting reaction condition: 80 DEG C of temperature are then passed to；Pressure
0.5MPa；H2/ hydroxy pivalin aldehyde molar ratio 5；Hydroxy pivalin aldehyde liquid hourly space velocity (LHSV) 2.0h-1It is reacted, product uses gas-chromatography
Analysis.
Embodiment 3
The nickel phosphide that 0.5g partial size is 30-60nm is loaded in fixed bed reactors, and the H at 200 DEG C2Locate in advance in stream
2h is managed, the hydroxy pivalin aldehyde ethanol solution that mass concentration is 11%, setting reaction condition: 100 DEG C of temperature are then passed to；Pressure
1MPa；H2/ hydroxy pivalin aldehyde molar ratio 10；Hydroxy pivalin aldehyde liquid hourly space velocity (LHSV) 1.0h-1It is reacted, product is using gas-chromatography point
Analysis.
Embodiment 4
The nickel phosphide that 0.5g partial size is 30-60nm is loaded in fixed bed reactors, and the H at 200 DEG C2Locate in advance in stream
2h is managed, the hydroxy pivalin aldehyde ethanol solution that mass concentration is 11%, setting reaction condition: 120 DEG C of temperature are then passed to；Pressure
1MPa；H2/ hydroxy pivalin aldehyde molar ratio 10；Hydroxy pivalin aldehyde liquid hourly space velocity (LHSV) 1.5h-1It is reacted, product is using gas-chromatography point
Analysis.
Embodiment 5
The nickel phosphide that 0.5g partial size is 30-60nm is loaded in fixed bed reactors, and the H at 200 DEG C2Locate in advance in stream
2h is managed, the hydroxy pivalin aldehyde ethanol solution that mass concentration is 11%, setting reaction condition: 100 DEG C of temperature are then passed to；Pressure
2MPa；H2/ hydroxy pivalin aldehyde molar ratio 10；Hydroxy pivalin aldehyde liquid hourly space velocity (LHSV) 1.0h-1It is reacted, product is using gas-chromatography point
Analysis.
Embodiment 6
The nickel phosphide that 0.5g partial size is 30-60nm is loaded in fixed bed reactors, and the H at 200 DEG C2Locate in advance in stream
2h is managed, the hydroxy pivalin aldehyde ethanol solution that mass concentration is 11%, setting reaction condition: 100 DEG C of temperature are then passed to；Pressure
3MPa；H2/ hydroxy pivalin aldehyde molar ratio 5；Hydroxy pivalin aldehyde liquid hourly space velocity (LHSV) 2.0h-1It is reacted, product is using gas-chromatography point
Analysis.
Embodiment 7
The hydroxy pivalin aldehyde ethanol solution that 20mL mass fraction is 11% is packed into together with 0.01g nano nickel phosphide
In 100mL autoclave, He and H is successively used2Replacement reaction kettle each 3 times, setting reaction condition: 100 DEG C of temperature；H2Pressure
0.5MPa；Time 5h.To which after reaction, solid catalyst uses gas chromatographic analysis using supercentrifuge separation, product.
Embodiment 8
The hydroxy pivalin aldehyde ethanol solution that 20mL mass fraction is 11% is packed into together with 0.02g nano nickel phosphide
In 100mL autoclave, He and H is successively used2Replacement reaction kettle each 3 times, setting reaction condition: 120 DEG C of temperature；H2Pressure
0.6MPa；Time 3h.To which after reaction, solid catalyst uses gas chromatographic analysis using supercentrifuge separation, product.
Embodiment 9
The hydroxy pivalin aldehyde ethanol solution that 20mL mass fraction is 11% is packed into together with 0.02g nano nickel phosphide
In 100mL autoclave, He and H is successively used2Replacement reaction kettle each 3 times, setting reaction condition: 120 DEG C of temperature；H2Pressure
0.8MPa；Time 3h.To which after reaction, solid catalyst uses gas chromatographic analysis using supercentrifuge separation, product.
Embodiment 10
The hydroxy pivalin aldehyde ethanol solution that 20mL mass fraction is 11% is packed into together with 0.02g nano nickel phosphide
In 100mL autoclave, He and H is successively used2Replacement reaction kettle each 3 times, setting reaction condition: 120 DEG C of temperature；H2Pressure
0.8MPa；Time 4h.To which after reaction, solid catalyst uses gas chromatographic analysis using supercentrifuge separation, product.
Embodiment 11
The hydroxy pivalin aldehyde ethanol solution that 20mL mass fraction is 11% is packed into together with 0.015g nano nickel phosphide
In 100mL autoclave, He and H is successively used2Replacement reaction kettle each 3 times, setting reaction condition: 150 DEG C of temperature；H2Pressure
0.8MPa；Time 2h.To which after reaction, solid catalyst uses gas chromatographic analysis using supercentrifuge separation, product.
The conversion ratio of hydroxy pivalin aldehyde obtained by above embodiments and the selectivity of neopentyl glycol are as shown in table 1.For implementing
The fixed bed reaction of example 2-6, institute's column data are i.e. active when reaction is carried out to 3h to reach stable sampling analysis result.As a result it shows
Show, the still reaction of either continuous fixed bed reaction or interval, nano nickel phosphide adds hydrogen preparation new in hydroxy pivalin aldehyde
Excellent catalytic hydrogenation property is shown in pentanediol, especially shows higher selectivity of neopentyl glycol.It is anti-in fixed bed
Ying Zhong, when reaction condition be 100 DEG C of temperature, pressure 2MPa, H2/ hydroxy pivalin aldehyde molar ratio 10, hydroxy pivalin aldehyde liquid hourly space velocity (LHSV)
1.0h-1When, available 99.8% hydroxy pivalin aldehyde conversion ratio and 99.5% selectivity of neopentyl glycol.In still reaction
In, when nickel phosphide and hydroxy pivalin aldehyde mass ratio 1:110,120 DEG C of temperature, H2Pressure 0.8MPa can be with when the reaction time is 4h
99.6% hydroxy pivalin aldehyde conversion ratio and 99.4% selectivity of neopentyl glycol are obtained simultaneously.Under preferably reaction condition,
The technique can obtain 99% or more neopentyl glycol yield.In addition, we, which have also investigated the catalyst, is preparing neopentyl glycol
Stability in reaction.In continuous fixed bed reaction, under the conditions of embodiment 5, catalyst is used continuously 480 hours, under activity
Range of decrease degree is within 2%.In batch tank reaction, under the conditions of embodiment 10, catalyst is multiplexed 30 times, and active fall exists
Within 3%, micro loss (~2% loss late) when among these including catalyst recycling.Illustrate nano nickel phosphide catalyst
It is with good stability.
1 nickel phosphide of table catalysis hydroxy pivalin aldehyde is hydrogenated to neopentyl glycol performance
| Embodiment | Hydroxy pivalin aldehyde conversion ratio (%) | Selectivity of neopentyl glycol (%) |
| 2 | 88.2 | 99.6 |
| 3 | 97.1 | 99.2 |
| 4 | 99.4 | 99.3 |
| 5 | 99.8 | 99.5 |
| 6 | 99.1 | 99.6 |
| 7 | 96.1 | 99.7 |
| 8 | 97.7 | 99.5 |
| 9 | 98.9 | 99.4 |
| 10 | 99.6 | 99.4 |
| 11 | 99.8 | 99.0 |
Claims (10)
1. a kind of method that catalytic hydrogenation prepares neopentyl glycol, it is characterised in that: by hydroxy pivalin aldehyde urging in nano nickel phosphide
Under change effect, add hydrogen that neopentyl glycol is made.
2. the method that catalytic hydrogenation as described in claim 1 prepares neopentyl glycol, it is characterised in that: the partial size of nano nickel phosphide
For 30-60nm.
3. the method that catalytic hydrogenation as claimed in claim 1 or 2 prepares neopentyl glycol, it is characterised in that: using continuous fixed
Bed reaction: nano nickel phosphide is loaded in fixed bed reactors, and the H at 200 ± 10 DEG C22 ± 0.1h is pre-processed in stream, so
It is passed through the hydroxy pivalin aldehyde ethanol solution that mass concentration is 11 ± 2% afterwards, temperature is 80-130 DEG C, pressure is 0.5-3MPa's
Under the conditions of react, be made neopentyl glycol.
4. the method that catalytic hydrogenation as claimed in claim 3 prepares neopentyl glycol, it is characterised in that: H2With hydroxy pivalin aldehyde
Molar ratio is 5-20；Hydroxy pivalin aldehyde liquid hourly space velocity (LHSV) is 0.5-2.0h-1。
5. the method that catalytic hydrogenation as claimed in claim 1 or 2 prepares neopentyl glycol, it is characterised in that: use batch tank
Reaction: the hydroxy pivalin aldehyde ethanol solution that mass concentration is 11 ± 2% is packed into autoclave together with nickel phosphide, is successively used
He and H2Replacement reaction kettle, and be 100-150 DEG C, H in temperature2Pressure reacts 2-5h under conditions of being 0.5-0.8MPa, and centrifugation removes
Go catalyst to get neopentyl glycol.
6. the method that catalytic hydrogenation as claimed in claim 5 prepares neopentyl glycol, it is characterised in that: nano nickel phosphide and hydroxyl
The mass ratio of neovaleraldehyde is 1:(110-200).
7. the method that catalytic hydrogenation as claimed in claim 1 or 2 prepares neopentyl glycol, it is characterised in that: nano nickel phosphide is pressed
The following steps synthesis: nickel chloride, sodium dihydric hypophosphite and cetyl trimethylammonium bromide are dissolved in ethylene glycol solution, and will
Mixture is heat-treated under return stirring state in oil bath, is then washed to product, vacuum drying is to get nanometer phosphorus
Change nickel.
8. the method that catalytic hydrogenation as claimed in claim 7 prepares neopentyl glycol, it is characterised in that: nickel chloride and hypophosphorous acid two
The molar ratio of hydrogen sodium is 1:(2-5), the molar ratio of nickel chloride and cetyl trimethylammonium bromide is 1:(1-3).
9. the method that catalytic hydrogenation as claimed in claim 7 prepares neopentyl glycol, it is characterised in that: the temperature of oil bath heat treatment
It is 150-170 DEG C, time 2-5h.
10. the method that catalytic hydrogenation as claimed in claim 7 prepares neopentyl glycol, it is characterised in that: washing methods is to use
Alcohol-water mixed solution is stripped 24-36h, wherein the volume ratio of second alcohol and water is 1:(1-2).
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| CN107970940A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | Nickel system hydroxy pivalin aldehyde Hydrogenation for neopentyl glycol catalyst and preparation method |
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| CN1286673A (en) * | 1997-12-30 | 2001-03-07 | 奈斯特化学公司 | Process for preparation of neopentyl glycol |
| TW486461B (en) * | 1999-09-29 | 2002-05-11 | Nanya Plastics Corp | Manufacture of neopentyl glycol |
| US6268539B1 (en) * | 1999-10-07 | 2001-07-31 | Nan Ya Plastics Corporation | Manufacturing method of neopentyl glycol |
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