A kind of preparation method of hydroxyl spy valeral, and its in terms of neopentyl glycol preparation
Using
Technical field
The present invention relates to a kind of preparation method of hydroxyl spy valeral, and its application in terms of neopentyl glycol preparation.
Background technology
Hydroxyl spy valeral (popular name is also referred to as hydroxy pivalin aldehyde, and IUPAC is named as 2,2- pentaldols, and 2,2-
Dimethyl-3-hydroxypropanal, abbreviation HPA), its structure isIt is synthesis 2,2- dimethyl -1,3-
The intermediate product of propane diols.
It is production technology current at present that condensation method, which prepares HPA,:Under the catalysis of inorganic base or trimethylamine, formaldehyde and different
Butyraldehyde carries out condensation reaction and obtains HPA.Industrial generally use formalin and isobutylaldehyde are raw material at present, with caustic soda or three
Ethamine synthesizes HPA for catalyst.When the sodium hydrate aqueous solution that concentration is 30~40wt.% is catalyst, yield is condensed
For 80~85%;When the use of triethylamine being catalyst, condensation yield can be more than 90%, but catalyst amount is big.
US5146012A uses 5~10wt.% triethylamines, and needs separator to recycle, and reaction temperature is inclined
The degree that height causes raw material that disproportionated reaction occurs is higher, and the organic acid of generation and triethylamine are reacted in subsequent handling to be formed
Salt, it is difficult to separate, cause the extra consumption of triethylamine.
Therefore find efficient approach to be applied to prepare hydroxyl spy's valeral and be of great significance tool, so as to prepare work
Skill simplifies, and improves the conversion ratio of raw material and the selectivity of product, and it is big to evade catalyst amount, difficult separation and recycling, reaction temperature
The shortcomings of higher.
(popular name is neopentyl glycol to 2,2-dimethyl-1,3-propanediol, Neopentyl glycol, abbreviation NPG, its structure
For), it is a kind of important chemical intermediate.Its mainly for the production of unsaturated-resin, polyester powder coating,
Oil-free alkyd resin, polyurethane foam plastics, the plasticizer of elastomer, synthesis plasticizer, surfactant, insulating materials, print
Brush ink, polymerization inhibitor, synthesis aeroengine oil oil dope etc., and also applied in pharmaceuticals industry.Meanwhile NPG is still
Excellent solvent, the selection available for aromatic hydrocarbons and cycloalkyl hydrocarbon separate.
The industrialized process for preparing of NPG is broadly divided into discrimination method and two kinds of hydrogenation method prepares road using HPA as raw material at present
Line.
Discrimination method refer to HPA under strongly alkaline conditions, with formaldehyde occur Canizaro disproportionated reaction, HPA by formaldehyde also
It is primary into NPG, and formaldehyde is then oxidized to formic acid, and sodium formate is neutralized into through liquid caustic soda.In discrimination method technique, the receipts of process are disproportionated
Rate is 88~90%, and process overall yields are preferably 74%.Discrimination method makees reducing agent with formaldehyde, consumes more formaldehyde and liquid caustic soda, former
Material list consumption is big;Use alkali catalyst, it is difficult to recycle, generation liquid also needs to neutralize separation, easy etching apparatus;By-product is largely low
The sodium formate of value and the production waste water for being about three times in product quality, and sodium formate micro in product has very the quality of product
It is big to influence;Reaction process is complicated, production cycle length.Therefore at abroad, discrimination method has gradually been hydrogenated method substitution;Domestic early stage
NPG devices are based on discrimination method, BASF Jilin Chemical neopentyl glycol Co., Ltd and create NPG devices in recent years that early stage sets up
Company, uses hydrogenation method production NPG instead.
Hydrogenation method is under catalyst, HPA and hydrogen is reacted and is prepared NPG.For industrialization cost consideration, hydrogenation
The HPA crude products that method uses HPA to be isobutylaldehyde, the condensation reaction solution of formaldehyde removes formaldehyde, isobutylaldehyde, catalyst and water.Formaldehyde
A large amount of accessory substance generations, predominantly neopentyl glycol acetals are inevitably had under condensation catalyst effect with isobutylaldehyde
Compound and Hydroxypivalyl hydroxypivalate, wherein acetal compound are mainly neopentyl glycol formal and neopentyl glycol contracting
Hydroxyl spy's valeral.Such accessory substance in HPA crude products is relatively stable, it is not easy to decomposes, easily brings hydrogenation to be not thorough, separates and be stranded
The problems such as difficult, reduction product yield and quality;If preparing NPG with sterling HPA repeated hydrogenations, and the purification of HPA crude products can be increased
Cost, and since the side reaction of HPA purification process causes byproduct content further to increase, reduce final NPG yields.
Cupric oxide/the copper chromite catalyst promoted in US4855515 using manganese oxide, but catalytic activity is low, hydrogenation temperature
Degree causes to have 5% or so HPA to decompose at 160~170 DEG C, and also more than 3% 3-hydroxypivalic acid neopentyl glycol ester not
Energy hydro-conversion is NPG, and selectivity is low.
CN200910201434.7 prepares NPG using copper system hydrogenation catalyst, but it can not be by acetal and unreacted reactant
Expect isobutylaldehyde separation, and use Crystalline extraction method, extract and separate efficiency is low.
CN201110187424.X prepares a kind of copper-based catalysts containing zinc, aluminium and manganese, and processing contains 3-hydroxypivalic acid
The hydrogenating materials of neopentyl glycol monoesters, the conversion ratio of Hydroxypivalyl hydroxypivalate is up to 52%.
CN201210227352.1 prepares a kind of copper-based catalysts promoted containing rhenium, zinc, titanium, zirconium and hafnium, and processing contains
The hydrogenating materials of Hydroxypivalyl hydroxypivalate, still contain 3-hydroxypivalic acid neopentyl glycol single in obtained reaction product
Ester is undecomposed, influences NPG yields, and untreated neopentyl glycol acetal compound.
In conclusion in the prior art, neopentyl glycol acetal compound can not be converted into NPG, 3-hydroxypivalic acid new penta
Diol monoester is unable to complete hydrogenation and is converted into NPG, and the hydrogenation of Hydroxypivalyl hydroxypivalate will be difficult to HPA, although right
Catalyst has carried out a degree of improvement, but in the case where reducing the disposal ability of catalyst, in hydrogenation products still
Residual hydroxy groups pivalic acid neopentyl glycol monoesters, causes NPG loss of yield, can not improve yield.
In epoxy compound compound carbonylation ring-opening reaction, hydroformylation reaction is always one of hot spot studied, it is provided
A kind of cheap approach prepares beta-hydroxy aldehyde;Beta-hydroxy aldehyde is a kind of formal intersection hydroxyl between two kinds of fatty aldehydes
Aldehyde product, is a kind of organic synthesis intermediate for extremely having potential value.
Early in 1963 just it has been reported that epoxide and HCo (CO)4It can obtain acyl carbonyl cobalt under CO atmosphere
The compound of type, the material are considered as the reactive intermediate of hydroformylation reaction.Yokokawa etc. is clearly demonstrated
Under 80 DEG C of conditions above, propylene oxide hydroformylation reaction can generate beta-hydroxy n-butanal;With Co2(CO)8For catalyst, but
Reaction temperature preferably must be held between 80~100 DEG C.When less than 80 DEG C, reaction will not occur;When higher than 100 DEG C, isomerization
The reaction of generation acetone just occupies main status, and with other side reactions.
In the industrial production, the hydroformylation of ethylene oxide is also the industrialization of currently the only epoxide hydroformylation
Project.1,3-PD can be obtained after product beta-hydroxy aldehyde hydrogenation to the hydroformylation reaction of ethylene oxide, it is
Synthesize the indispensable raw material of polypropylene terephthalate (PTT) new type polyester fiber.Cobalt, rhodium etc. are metal complex catalyzed
Agent shows preferable catalytic performance in epoxide hydroformylation reaction.However, it is often accompanied with during the reaction
The generation of some side reactions, such as isomerization and the reduction of carbonyl functional group hydrogenation, or the dimerization of beta-hydroxy aldehyde.
The reaction system more excellent therefore, it is necessary to find some performances, including substrate, catalyst etc., to suppress side reaction
Generation, more efficiently prepare HPA, and further prepare NPG etc..
The content of the invention
It is an object of the present invention to provide a kind of preparation method of hydroxyl spy valeral, this method Atom economy
It is good, low raw-material cost, no waste water generation, and there is preferable yield.
Another object of the present invention is to provide a kind of application of hydroxyl spy valeral in terms of neopentyl glycol preparation, the application
Method has been evaded the drawbacks of current conventional method, and reaction system is simple, and prospects for commercial application is excellent.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is as follows:
A kind of preparation method of hydroxyl spy valeral, it is characterised in that prepared using epoxide hydroformylation reaction, bag
Include following synthesis and separating step:
A) added under inert gas (such as nitrogen, argon gas) atmosphere into reaction kettle epoxy iso-butane, major catalyst and
Co-catalyst, is warming up to 20~50 DEG C, stirs 0.5~2h catalyst-solvents, is uniformly mixed and obtains reaction solution;
B) reaction solution in reaction kettle is warming up to 70~150 DEG C, preferably 90~100 DEG C, be passed through relative pressure for 1~
The synthesis gas of 20MPa, preferably 9~10MPa are reacted, and the reaction time is 1~10h, preferably 5~6h;The synthesis gas is H2
It is 1 with CO molar ratios:1 gaseous mixture;Keep reactor temperature, pressure constant in reaction process, return to after reaction
Normal pressure, obtains reaction solution H;
C) reaction solution H obtained by step b) is distilled, obtains hydroxyl spy's valeral.
Reaction equation is as follows:
The present invention method in, the major catalyst described in step a) is the compound containing cobalt or rhodium, preferably be selected from rhodium carbonyl,
One or both of rhodium acetate, rhodium caprylate, acetylacetone,2,4-pentanedione rhodium, acetylacetone,2,4-pentanedione rhodium carbonyl, carbonyl cobalt are a variety of, more preferably acetic acid
One or both of rhodium, rhodium caprylate, carbonyl cobalt are a variety of.Major catalyst dosage for epoxy iso-butane weight 0.0005~
1wt.%, preferably 0.01~0.1wt.%.
In the method for the present invention, the co-catalyst described in step a) is one or both of following compounds or a variety of:
Aluminium chloride, iron chloride, zinc chloride, boron trifluoride, butyl titanate, stannous oxalate, the fluoroform of columbium pentachloride and lanthanide series
The preferred trifluoromethanesulfonic acid lanthanum of fluoroform sulphonate of sulfonate, wherein lanthanide series, trifluoromethanesulfonic acid cerium, trifluoromethanesulfonic acid neodymium,
Trifluoromethanesulfonic acid samarium;One or both of the preferred aluminium chloride of co-catalyst, boron trifluoride, butyl titanate, trifluoromethanesulfonic acid lanthanum
It is or a variety of.Co-catalyst dosage is the 0.001~0.5wt.%, preferably 0.01~0.1wt.% of epoxy iso-butane weight.
Another object of the present invention is to provide the reaction solution H of above method synthesis answering in terms of neopentyl glycol preparation
With concrete technical scheme is as follows:
After above method step b) obtains reaction solution H, it is passed through hydrogen progress hydrogenation reaction and obtains hydrogenation reaction solution, reaction temperature
70~150 DEG C of degree, is passed through hydrogen 1~20MPa of relative pressure by preferably 90~100 DEG C, preferably 8~10MPa, and the reaction time 1~
10h, preferably 5~6h;Hydrogenation reaction solution is distilled, obtains neopentyl glycol product.
Compared with prior art, the present invention have the following advantages:
Using epoxy iso-butane as raw material, hydroformylation reaction is carried out with synthesis gas, has effectively evaded in common itinerary and having adopted
The acetal by-product brought with formaldehyde and isobutylaldehyde condensation;Epoxy iso-butane source can be our company's petrochemical equipment by-product, close
Derived from a wealth of sources into gas, cost of material can be controlled effectively;Whole reaction of atomic economy is high, and no conventional condensation reaction can produce useless
Water and raw material formaldehyde introduce waste water, have significantly saved cost for wastewater treatment;Using epoxy iso-butane as hydroformylation substrate, pass through
The selection and adjustment of antigravity system, can obtain HPA in high yield, and due to HPA molecular structure properties, hydroxyl β carbon and aldehyde
Hydrogen-free on base α carbon, will not be as the product after the conventional epoxy compounds hydroformylation such as ethylene oxide, propylene oxide is due to hydroxyl β
Easily it is dehydrated there are active hydrogen on carbon and aldehyde radical α carbon or dimerization, poly, restrained effectively the generation of side reaction, improve
The yield of HPA;In the presence of co-catalyst, the carbonium ion that epoxy iso-butane tertiary carbon position is formed is more stable, so nucleophilic ring opening
Reaction will be controlled mainly by electronic effect, and after co-catalyst activation epoxy, carbonylating catalyst tends to attack epoxy iso-butane
Polysubstituted carbon atom, so as to substantially increase the selectivity of the special valeral structure of generation, improve ultimate yield, can reach
90~94%.
Purification prepares NPG after being directly catalyzed HPA reaction solutions hydrogenation with homogeneous hydroformylation catalyst, has evaded conventional method
The complicated technology that first purification back end hydrogenation purifies again, and reactor apparatus need not be increased and additionally add hydrogenation catalyst, effectively
Plant construction investment and hydrogenation catalyst cost are saved in ground.
Embodiment
With reference to embodiment, the present invention is further illustrated, it is necessary to which explanation, embodiment are not formed to this
The limitation of the claimed scope of invention.
Example analytical instrument and method are as follows:
Gas chromatograph:Agilent-7820;
Gas chromatographic column:The DB-5 capillary columns of 0.25mm × 30m, detector FID, gasify 280 DEG C of room temperature, post case temperature
280 DEG C of degree, 300 DEG C of fid detector temperature, argon gas carrier stream amount 2.1mL/min, hydrogen flowing quantity 30mL/min, air mass flow
400mL/min, 1.0 μ L of sample size.Usable floor area normalization method calculates the conversion ratio of alkene and the selectivity of product.Heating schedule:
40 DEG C of column temperature is preheated to, keeps 5min, the speed of 15 DEG C/min rises to 280 DEG C from 40 DEG C, keeps 10min.Wherein epoxy isobutyl
Alkane retention time 1.8min, hydroxyl spy valeral retention time 4.8min, neopentyl glycol retention time 5.5min.
Embodiment 1
The preparation of HPA
1kg epoxies iso-butane, 0.05g rhodium caprylates and 0.1g tri- are added into the pressure-resistant stirred autoclaves of 2L under nitrogen atmosphere
Boron fluoride, is warming up to 50 DEG C of stirring 0.5h under nitrogen atmosphere, and catalyst all dissolves at this time.By reaction solution liter in reaction kettle
After warm to 90 DEG C, H is passed through2:CO molar ratios 1:1 synthesis gas to reaction kettle relative pressure is 10MPa, when under reacting kettle inner pressure
It is 10MPa that synthesis gas to system pressure is supplemented during drop, keeps reactor temperature, pressure constant, gas phase is sampled after reacting 6h
Chromatography epoxy iso-butane conversion ratio 99.2%, HPA selectivity 91%, reaction terminates.It is right after reaction kettle pressure release to normal pressure
Gained reaction solution carries out air-distillation, cut when collecting 92~93 DEG C, as HPA, yield 90.3%.
The preparation of NPG
By the preparation process of HPA in embodiment 1, reaction terminates, by after reaction kettle pressure release to normal pressure, reaction solution to be warming up to
100 DEG C, it is 10MPa to be filled with hydrogen to reaction kettle relative pressure immediately, when reacting kettle inner pressure declines, that is, hydrogen make-up to body
It is that pressure is 10MPa, keeps reactor temperature, pressure constant, gas chromatographic analysis HPA conversion ratios is sampled after reacting 6h
99%, NPG selectivity 98%.Air-distillation is carried out to gained reaction solution, cut when collecting 210 DEG C, is white when being cooled to room temperature
Color crystal, is NPG.
Embodiment 2
The preparation of HPA
1kg epoxies iso-butane, 0.5g rhodium carbonyls and 5g metatitanic acids are added into the pressure-resistant stirred autoclaves of 2L under nitrogen atmosphere
Butyl ester, is warming up to 20 DEG C of stirring 1.5h under nitrogen atmosphere, and catalyst all dissolves at this time.Reaction solution in reaction kettle is heated up
To after 150 DEG C, H is passed through2:CO molar ratios 1:1 synthesis gas to reaction kettle relative pressure is 7MPa, when reacting kettle inner pressure declines
When to supplement synthesis gas to system pressure be 7MPa, keep reactor temperature, pressure constant, gas-chromatography sampled after reaction 4h
Epoxy iso-butane conversion ratio 99.4% is analyzed, HPA selectivity 92%, reaction terminates.After reaction kettle pressure release to normal pressure, to gained
Reaction solution carries out air-distillation, cut when collecting 92~93 DEG C, as HPA, yield 91.4%.
The preparation of NPG
By the preparation process of HPA in embodiment 2, reaction terminates, by after reaction kettle pressure release to normal pressure, reaction solution to be cooled to
70 DEG C, it is 20MPa to be filled with hydrogen to reaction kettle relative pressure immediately, when reacting kettle inner pressure declines, that is, hydrogen make-up to system
Pressure is 20MPa, keeps reactor temperature, pressure constant, and gas chromatographic analysis HPA conversion ratios 97% are sampled after reacting 3h,
NPG selectivity 99%.Gained reaction solution is evaporated under reduced pressure, cut when relative pressure -0.05MPa collects 185~190 DEG C,
It is white crystal when being cooled to room temperature, is NPG.
Embodiment 3
The preparation of HPA
1kg epoxies iso-butane, 10g carbonyl cobalts and 1g fluoroforms are added into the pressure-resistant stirred autoclaves of 2L under nitrogen atmosphere
Sulfonic acid lanthanum, is warming up to 40 DEG C of stirring 1h under nitrogen atmosphere relative pressure 0.5MPa, and catalyst all dissolves at this time.Will reaction
After reaction solution is warming up to 70 DEG C in kettle, H is passed through2:CO molar ratios 1:1 synthesis gas to reaction kettle relative pressure is 20MPa, when anti-
It is 20MPa to answer and synthesis gas to system pressure is supplemented when pressure declines in kettle, keeps reactor temperature, pressure constant, reaction
Gas chromatographic analysis epoxy iso-butane conversion ratio 96% is sampled after 6h, HPA selectivity 97.6%, reaction terminates.Reaction kettle is let out
After being depressed into normal pressure, air-distillation is carried out to gained reaction solution, cut when collecting 92~93 DEG C, as HPA, yield 93.7%.
The preparation of NPG
By the preparation process of HPA in embodiment 3, reaction terminates, by after reaction kettle pressure release to normal pressure, reaction solution to be warming up to
150 DEG C, it is 1MPa to be filled with hydrogen to reaction kettle relative pressure immediately, when reacting kettle inner pressure declines, that is, hydrogen make-up to system
Pressure is 1MPa, keeps reactor temperature, pressure constant, and gas chromatographic analysis HPA conversion ratios 98% are sampled after reacting 10h,
NPG selectivity 97%.Air-distillation is carried out to gained reaction solution, cut when collecting 210 DEG C is brilliant for white when being cooled to room temperature
Body, is NPG.