CN109790630A - For manufacturing the electrochemical method of methyl ethyl ketone - Google Patents
For manufacturing the electrochemical method of methyl ethyl ketone Download PDFInfo
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- CN109790630A CN109790630A CN201780055234.8A CN201780055234A CN109790630A CN 109790630 A CN109790630 A CN 109790630A CN 201780055234 A CN201780055234 A CN 201780055234A CN 109790630 A CN109790630 A CN 109790630A
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Abstract
The present invention provides a kind of by using the high hydrogen overvoltage cathode being made by lead electroreduction 3-hydroxy-2-butanone and the method for preparing methyl ethyl ketone in an aqueous medium, method includes the following steps: a) by the way that 3-hydroxy-2-butanone and aqueous medium and soluble supporting electrolyte mixes in such medium and are formed solution and b) by using DC power supply with 500 to 5000A/m2Current density apply voltage between anode and the cathode, the solution is continuously or non-continuously electrolysed in electrochemical reactor.
Description
This application claims the equity of on September 14th, the 2016 European patent application EP16382424.6 submitted.
Technical field
It is electric in the solution the present invention relates to using high hydrogen overvoltage cathode to pass through in cellular-type and non-separated electrolysis bath
Reduction 3-hydroxy-2-butanone (also referred to as 3-Hydroxybutanone) and manufacture the electrochemical method of methyl ethyl ketone (also referred to as 2- butanone and MEK),
The solution is formed by by 3-hydroxy-2-butanone and aqueous medium and soluble supporting electrolyte mixes in such medium and.
Background technique
MEK is the important chemical for the solvent being industrially widely used as in vinylite and China Synthetic Rubber Industry.Mesh
Before, MEK by under the pressure at 400-500 DEG C and lower than 0.4MPa and on copper and Zinc oxide catalytic to 2-butanol dehydrogenation work
Industry production, such as disclosed in US4075128.Other chemical methodes described in the prior are as US5506363 institute is public
That opens carries out Wacker liquid phase oxidation to butylene under about 85 DEG C and 0.69MPa；And such as Zhao " Catalytic
dehydration of 2,3-butanediol over P/HZSM-5:effect of catalyst,reaction
temperature and reactant configuration on rearrangement products”,RSC Adv.,
That is reported in 2016, Vol.14, pp.16988-16995 is dehydrated 2,3- butanediol using acidic catalyst.
Other than since the 2,3-butanediol that can be obtained by the fermentation of sugar, these methods are related to serious ring
It bears and uses non-renewable fossil resource as raw material in border.However, a kind of last method is run at high temperature, therefore energy
It consumes very high.Therefore, it is necessary to manufacture MEK since renewable raw materials and can work under low temperature and low pressure free of contamination new
Method.
US3247085 discloses the electrochemical method that a kind of electroxidation by 1- butylene prepares MEK.
Baizer etc. " Electrochemical conversion of 2,3-butanediol to 2-butanone
in undivided flow cells:a paired synthesis",J.Appl.Electrochem,1987,Vol.14,
Pp.197-208 discloses the method that the 2,3-butanediol in about 10% aqueous solution is converted to MEK, by such as lower section
Formula carries out: making the 2,3-butanediol in about 10% aqueous solution by porous anode, passes through electroluminescent life in the porous anode
At NaBrO its selectance is oxidized to 3-hydroxy-2-butanone, be then pumped into porous cathode, be reduced at the porous cathode
MEK.3-hydroxy-2-butanone formed in solution is at cathode by electroreduction and aoxidizing 2,3- butanediol with the NaBrO of electroluminescent generation
At MEK.However, this method is due to its 20A/m2Low-down current density (be far below at least 500A/m2To about 5000A/m2
Useful industrial density) without industrial applicibility.Therefore, the methods of Baizer causes productivity very poor, needs a huge sum of money
Investment.From the point of view of environmental point of view, another strong current disadvantages of this method are using the cathode based on Hg and to be electrolysed
There are NaBrO in solution.In addition, Baizer etc. points out that current density is increased above 20A/m2It will lead to more H2It generates,
Cause current efficiency low and the high bath voltage as caused by the gas of electrolyte bath capture, is inferred to match reaction and answers
It should be in low current density (10 or 20A/m2) under operation to obtain relatively high current efficiency.
WO2016097122 discloses a kind of by using porous Pt or Ni cathode electroreduction 3- hydroxyl in an aqueous medium
Butanone is come the method for preparing 2,3- butanediol.In comparative example 1, MEK by usingGDL-24BC electro-reduction
3-Hydroxybutanone and obtain, selectance 64.0%, for 3-Hydroxybutanone conversion ratio be 75.7%.However, as with work
The productivity of the directly related key parameter of industry productivity, i.e., every m per hour2Electrode (cathode) area in the MEK thousand that generates
Grams (kg-MEK/h/m2)(PMEKHigher, capital investment is lower), it is low for actual use.
Therefore, there is still a need for it is a kind of industrially can scale method, this method allows to obtain with the productivity improved
MEK。
Summary of the invention
Inventor has discovered that a kind of new method for preparing MEK, overcomes and/or minimizes and discloses in the prior art
Method some disadvantages.Specifically, provide the economy for producing MEK and industrially can scale method, tool
There is productivity more higher than the productivity that the method by the prior art obtains.Because from example as can be seen that new by this
Method, under room temperature and environmental pressure, under the current density needed for commercial viability, by 3-hydroxy-2-butanone electroreduction and to show
It writes high productivity and obtains MEK in aqueous solution.
Therefore, the present invention relates to a kind of by using the high hydrogen overvoltage cathode being made by lead electroreduction in an aqueous medium
3-hydroxy-2-butanone and the method for preparing methyl ethyl ketone (MEK), the described method comprises the following steps:
A) it is formed and soluble supporting electrolyte mixes by 3-hydroxy-2-butanone with aqueous medium and in such medium molten
Liquid, and
B) by using DC power supply with 500 to 5000A/m2, particularly 2500,2000,1500 or 1000A/m2Electric current
Density applies voltage between anode and the cathode, and the solution is continuously or non-continuously electrolysed in electrochemical reactor.
Specific embodiment
It is easy to be reduced in ontology catholyte as it is used herein, " hydrogenation catalyst " refers to catalysis
Group is by the catalyst of hydrogen reduction, and wherein hydrogen first passes through electroreduction water and electroluminescent generation in the cathode in advance.Therefore, in hydrogenating catalytic
In the presence of agent, electrolysis is readily able to the direct electroreduction of the group being reduced for generating hydrogen.The example of hydrogenation catalyst
It is carried noble metal (such as support type Pt, Pd, Ru, Ir and Rh), thunder Buddhist nun Ni and support type Ni.
3-hydroxy-2-butanone has asymmetric carbon, therefore it is chiral molecules.Any stereoisomer and its mixture
Raw material as the method for the present invention.Therefore, in the entire present invention, term 3-hydroxy-2-butanone includes its enantiomer and its any ratio
Mixture, such as racemic mixture or the enantiomer of its enantiomter enrichment mixture.
As disclosed in ES2352633, second can be obtained and the aqueous solution of glucose, syrup or molasses ferments
Acyloin, wherein the microorganism for carrying out bioconversion is the mutant bacteria of Lactococcus lactis (Lactococcus lactis lactis)
Strain.By this method, the manufacturing cost of 3-hydroxy-2-butanone is sufficiently low, so that be economically feasible from 3-hydroxy-2-butanone electro synthesis MEK.
As used herein, term " electrolytic cell ", " electrochemical cell " and " electrochemical reactor " is interchangeable.
As used herein, " aqueous medium " refers to the water or water and complete or partial water-miscible solvent of 100 weight %
Mixture, in the mixture, the amount of water is 50 weight % to 99 weight %, especially 70 weight % to 99 weight %, more
Especially 85 weight % to 99 weight %.Suitable fully and partially water-miscible solvent be under electrolytic condition of the invention not
Has electroactive solvent.The example of the solvent includes but is not limited to alcohols such as methanol, ethyl alcohol, propyl alcohol and isopropanol；Ethers
Such as tetrahydrofuran and dioxanes；With nitrile such as acetonitrile.
As described above, the present invention relates to by using the high hydrogen overvoltage cathode being made by lead electroreduction in an aqueous medium
3-hydroxy-2-butanone and the method for preparing MEK.Particularly, which carries out in the case where hydrogenation catalyst is not present.
In a specific embodiment, cathode material is flat lead, or the lead being deposited in porous carrier, institute
Stating porous carrier is, for example, carbon felt, carbon foam or similar material.
Electrochemical reactor for the method for the present invention can be known to the skilled in the art any one, such as tank
Formula electrochemical reactor or flow type filter press-type electrochemical reactor.In a specific embodiment of the method for the present invention, electricity
Chemical reactor is flow type filter press-type electrochemical reactor.Electrochemical reactor can be cellular-type or non-cellular-type, most
Latter construction is most preferably, because it can reduce power consumption and reduce capital investment.If anti-using divided electrochemical
Device is answered, then anode and cathode is by preventing anolyte (solution without 3-hydroxy-2-butanone supplied by anodal compartment, such as sulphur
Aqueous acid) and the material separates of catholyte (pass through cathodic compartment supply the solution containing 3-hydroxy-2-butanone) mixing open, simultaneously
Ion flow is allowed to transmit electric current in the solution.Cation-exchange membrane is most preferred point for divided electrochemical reactor
Barrier material.The example of cation-exchange membrane include but is not limited toAny one of those of brand sales, such asN-324 andN-424。
In a specific embodiment of the method for the present invention, as anode material (anode), in the method for the invention
Use carbon steel, the platinum being supported on titanium (Pt/Ti) and iridium base(anode of dimensionally stable).They can be with non-porous flat
Flat form and as perforated material (such as net, metallic screen, thin slice (lamellae), forming net (shaped webs) and grid)
It uses.
According to the present invention by 3-hydroxy-2-butanone electroreduction at MEK is carried out in the presence of supporting electrolyte, described in addition
Supporting electrolyte is to adjust the conductivity of electrolytic solution and/or the selectance of control reaction.In a tool of method of the invention
In body embodiment, based on the gross mass of the solution, the amount of supporting electrolyte is usually adjusted to 0.1 weight % to 20 weights
Measure %, the level of particularly from about 1 weight % to about 15 weight %, more particularly about 5 weight % to about 10 weight %.In non-separation
The example of the supporting electrolyte of catholyte when formula electrolytic cell is neutralized for using separated electrolysis bath includes but is not limited to
The ammonium salt and alkali and alkaline earth metal ions salt and quaternary ammonium salt of inorganic acid (such as sulfuric acid, phosphoric acid and nitric acid), for example, tetraethyl
Ammonium bromide, etamon chloride and tetraethyl ammonium sulfate and tetrabutylammonium bromide, tetrabutylammonium chloride and tetrabutyl ammonium sulfate.
If method of the invention carries out in separated electrolysis bath, it to be used for the other supporting electrolyte of catholyte
It is the ammonium salt and alkali and alkali salt of hydrochloric acid, hydrobromic acid and hydrofluoric acid；Supporting electrolyte for anolyte includes
But it is not limited to the ammonium salt and alkali and alkaline earth metal ions salt of inorganic acid (such as sulfuric acid and phosphoric acid) and the inorganic acid.Therefore,
In a specific embodiment, method of the invention is to carry out in separated electrolysis bath, and the support of solution is formed with 3-hydroxy-2-butanone
Electrolyte is selected from the group being made of ammonium salt and alkali and alkaline earth metal ions salt, the quaternary ammonium salt and its mixture of inorganic acid, and
Supporting electrolyte for anolyte is non-oxidizable inorganic acid.
The pH of electrolyte in the non-separated electrolysis bath or pH of the catholyte in separated electrolysis bath can be 2.5
To 7.Therefore, in a specific embodiment of the method for the present invention, by by 3-hydroxy-2-butanone and aqueous medium and in such Jie
Soluble supporting electrolyte mixing in matter and the pH of solution formed are 2.5 to 7, especially 3 to 7, more particularly 4 to 7.PH tune
Section can be by adding suitable acid (such as phosphoric acid or sulfuric acid) or alkali (such as sodium hydroxide or potassium hydroxide) Lai Jinhang.If
PH is lower than 2.5, then the hydrogen as caused by the electroreduction of proton is precipitated, and current efficiency reduces.If pH is higher than 7, due to second idol
The selectance of the aldol condensation of relation by marriage and MEK, reaction becomes negatively affected.
Based on the total volume of solution to be electrolysed, to be electrolysed by by 3-hydroxy-2-butanone and aqueous medium and in such Jie
Soluble supporting electrolyte mixes in matter and the 3-hydroxy-2-butanone concentration in the solution of formation is at least 10g/L, especially at least 25g/
L, more particularly at least 50g/L, most particularly at least 100g/L.
In a specific embodiment of method of the invention, it is assumed that current efficiency is 100% (in every mole of 3-hydroxy-2-butanone
2 faraday), for being MEK by 3-hydroxy-2-butanone electroreduction and the amount of electric power that recycles is the 3-hydroxy-2-butanone conversion ratio for being used to obtain 100%
Theoretical amount 50% to 125%, more particularly 55% to 100%, most particularly 60% to 75%.
It is about 10 DEG C by the temperature that 3-hydroxy-2-butanone electroreduction is MEK in a specific embodiment of method of the invention
To 70 DEG C.Especially electrolysis temperature is room temperature.
In a specific embodiment, after the completion of electrolysis, MEK is separated by being evaporated in vacuo, and keeps water phase load new
Fresh 3-hydroxy-2-butanone is restored to be electrolysed to restore its initial concentration.
In a specific embodiment, it is continuously removed from aqueous medium in electrolytic process by being evaporated in vacuo
MEK.Therefore, the aqueous medium containing MEK being discharged from electrochemical reactor is heated to 40 DEG C to 50 DEG C of temperature, and is sent to vacuum
Evaporator, wherein MEK evaporation and condensation.The aqueous medium for exhausting MEk is cooled to electrolysis temperature in a heat exchanger, and sends back to
Electrochemical reactor, remaining 3-hydroxy-2-butanone is MEK by electroreduction wherein.When 3-hydroxy-2-butanone concentration is decreased below initial concentration
When 40% to 50% level, initial concentration is restored by adding fresh 3-hydroxy-2-butanone.
In another embodiment, in electrolytic process by using water-insoluble atent solvent (such as toluene,
Dimethylbenzene, t-butyl methyl ether and methyl iso-butyl ketone (MIBK)) liquid-liquid extraction, MEK is continuously removed from aqueous medium.Ability
Field technique personnel easily identify other suitable solvents.
In another embodiment, method of the invention carries out in following reactors:
I) electrochemical reactor；Or
Ii) at least two electrochemical reactor being connected in series, the series system to be produced by an electrochemical reactor
Raw solution is supplied to subsequent electrochemical reactor, which includes unreacted 3-hydroxy-2-butanone, MEK, aqueous medium and such
The mixture of soluble supporting electrolyte in medium.
If current density and circulation charge are electrochemical from first using the more than two electrochemical reactors being connected in series
Reactor is learned to decline to the last one electrochemical reactor.For example, if using two electrochemical reactors being connected in series,
Current density used in first electrochemical reactor is higher than current density used in the second electrochemical reactor；And it is opposite
The ratio that charge is recycled in the total electrical charge recycled by two electrochemical reactors, the first electrochemical reactor is higher than the second electricity
The ratio of circulation charge in chemical reactor.In this way, electric energy is more efficiently used for 3-hydroxy-2-butanone electroreduction being MEK.
In entire disclosure and claims, the variant of word " comprising " and the word is not intended to exclude other skills
Art feature, additive, ingredient or step.In addition, word " comprising " cover " by ... form " the case where.Following implement is provided
Example is in order to illustrate they are not intended to limit the present invention.In addition, the present invention covers as described herein specific and preferred implementation side
The all possible combinations of formula.
Embodiment
Embodiment 1
By 3-hydroxy-2-butanone (100g/L) and KH2PO4The aqueous solution (60mL) of (5 weight %) is by means of magnetic drive pump with 2L/min's
Flow velocity is recirculated through by the Ti support type yttrium oxide base DSA plate (20cm as anode2) composition cellular-type filters pressing electrolysis
The cathode chamber of slot, for separating anode and cathode roomN-324 cation-exchange membrane and lead plate as cathode
(20cm2).Interelectrode gap is 1.7cm.By means of another magnetic drive pump by the aqueous sulfuric acid of 5 weight % recirculated through sun
Pole room.Apply voltage between the anode and cathode by using DC power supply to make electric current (3A, 1500A/m2) circulation.Electrolysis exists
73.01 minutes (100% of the theoretical charge that 3-hydroxy-2-butanone converts completely, it is assumed that current efficiency is are kept under room temperature (20-25 DEG C)
100%).Initial catholyte pH is 4.32, and final pH is 3.75 (average pH is 4.04).After electrolysis, catholyte
The MEK of matter solution (64mL) 3-hydroxy-2-butanone containing 27.2g/L concentration and 40.8g/L concentration, as shown in HPLC.Therefore, 3-hydroxy-2-butanone
Conversion ratio is 71% (71% current efficiency), and MEK yield is 53.1% (53.1% current efficiency), leads to the selectance to MEK
(the ratio between yield and conversion ratio) is 74.9%.MEK productivity is 1.07kg MEK/h/m2。
Embodiment 2
In the same manner as in Example 1, but 3-hydroxy-2-butanone (100g/L), KH are used2PO4(5 weight %) and tetraethylammonium bromide (1 weight
Measure %) aqueous solution (60mL) be used as catholyte.The pH value of initial catholyte is 4.31, final ph 4.23
(average pH is 4.27).After electrolysis, 3-hydroxy-2-butanone and 46.7g/ of the catholyte solution (64mL) containing 25.1g/L concentration
The MEK of L concentration, as shown in HPLC.Therefore, 3-hydroxy-2-butanone conversion ratio is 73.2% (73.2% current efficiency), and MEK yield is
60.8% (60.8% current efficiency) causes to be 83.1% to the selectance of MEK.MEK productivity is 1.23kg MEK/h/m2。
Embodiment 3
In the same manner as in Example 1, but 3-hydroxy-2-butanone (100g/L), KH are used2PO4(5 weight %) and tetrabutylammonium bromide (0.5
Weight %) aqueous solution (60mL) be used as catholyte.The pH value of initial catholyte is 4.32, final ph 6.68
(average pH is 5.50).After electrolysis, 3-hydroxy-2-butanone and 38.7g/ of the catholyte solution (63mL) containing 11.7g/L concentration
The MEK of L concentration, as shown in HPLC.Therefore, 3-hydroxy-2-butanone conversion ratio is 87.8% (87.8% current efficiency), and MEK yield is
49.7% (49.7% current efficiency) causes to be 56.6% to the selectance of MEK.MEK productivity is 1.00kg MEK/h/m2。
Embodiment 4
In the same manner as in Example 1, but 3-hydroxy-2-butanone (100g/L), KH are used2PO4The aqueous solution (60mL) of (5 weight %) (is used
KOH is adjusted to pH 7.0) it is used as catholyte.Final ph is 6.97 (average pH is 6.99).After electrolysis, cathode electricity
The MEK of electrolyte solution (63mL) 3-hydroxy-2-butanone containing 21.8g/L concentration and 42.4g/L concentration, as shown in HPLC.Therefore, second is even
Relation by marriage conversion ratio is 77.1% (77.1% current efficiency), and MEK yield is 54.3% (54.3% current efficiency), is caused to MEK's
Selectance is 70.4%.MEK productivity is 1.10kg MEK/h/m2。
Embodiment 5
In the same manner as in Example 1, but 3-hydroxy-2-butanone (100g/L), KH are used2PO4The aqueous solution (60mL) of (5 weight %) (is used
Dense H2SO4It is adjusted to pH 3.07) as catholyte.Final ph is 2.64 (average pH is 2.86).After electrolysis, yin
The MEK of pole electrolyte solution (63mL) 3-hydroxy-2-butanone containing 20.6g/L concentration and 39.5g/L concentration, as shown in HPLC.Therefore,
3-hydroxy-2-butanone conversion ratio is 78.4% (78.4% current efficiency), and MEK yield is 50.6% (50.6% current efficiency), is caused pair
The selectance of MEK is 64.5%.MEK productivity is 1.02kg MEK/h/m2。
Embodiment 6
In the same manner as in Example 1, but 3-hydroxy-2-butanone (100g/L), KH are used2PO4The aqueous solution (60mL) of (5 weight %) (is used
KOH is adjusted to pH 5.5) it is used as catholyte, current density 1000A/m2(2A, electrolysis time is 109.6 minutes, corresponding
In the charge for being 100% relative to theoretical value).Final ph is 5.53.After electrolysis, catholyte solution (61mL) contains
There are the 3-hydroxy-2-butanone of 11.6g/L concentration and the MEK of 52.2g/L concentration, as shown in HPLC.Therefore, 3-hydroxy-2-butanone conversion ratio is 88.2%
(88.2% current efficiency), MEK yield are 64.7% (64.7% current efficiency), cause to be 73.4% to the selectance of MEK.
MEK productivity is 0.87kg MEK/h/m2。
Embodiment 7 (comparative example)
In the same manner as in Example 6, but use cadmium as cathode.Final ph is 5.51.After electrolysis, catholyte
The MEK of solution (63mL) 3-hydroxy-2-butanone containing 7.5g/L concentration and 45.6g/L concentration, as shown in HPLC.Therefore, 3-hydroxy-2-butanone converts
Rate is 92.1% (92.1% current efficiency), and MEK yield is 58.4% (58.4% current efficiency), leads to the selectance to MEK
It is 63.5%.MEK productivity is 0.79kg MEK/h/m2。
Embodiment 8,9 (comparative example), 10 (comparative examples)) and 11-24
These embodiments illustrate cathode material (embodiment 8,9 (comparative example), 10 (comparative examples) and 11-15), 3-hydroxy-2-butanone it is dense
Spend (embodiment 8,16 and 17；And 19 and 21), the influence of charge (embodiment 18-20) and temperature (embodiment 21-24).It uses
3-hydroxy-2-butanone (concentration specified in table 1) and KH2PO4The aqueous solution (60mL) of (concentration specified in table 1) (is adjusted to pH with KOH
5.5) it is used as catholyte, by making also charge circulation specified in table 1, is tested in the same manner as in Example 1.PH is
It 5.5 and is kept constant in entire electrolysis.As a result it is given in Table 1, wherein the meaning of symbol is as follows:
- E: electrolyte (catholyte for separated electrolysis bath)
- Q: charge, the percentage for the theoretical charge that acetate converts completely, it is assumed that current efficiency 100%,
- C: 3-hydroxy-2-butanone conversion ratio,
-SMEK: to the selectance of MEK,
-ηMEK: MEK current efficiency,
[3-hydroxy-2-butanone]i: initial 3-hydroxy-2-butanone concentration,
-[MEK]f: the final MEK concentration after electrolysis,
- Sigracet GDL-24BC/SS: by 20cm2Glued and load gas diffusion layers (SGL on stainless steel plate
Group, The Carbon Company),
Pb-X/GDL-24BC/SS: the Pb being electrodeposited on Sigracet GDL-24BC/SS, it measures as X μ g/cm2Geometric surface
Product.
- P:MEK productivity
Δ P: the productivity relative to comparative example 1 (%) increases (%)
Embodiment 25 (comparative example comes from WO2016097122)
By 3-Hydroxybutanone (101.1g/L), KH2PO4(2.5 weight %) and Na2SO4The aqueous solution of (4 weight %)
(60mL) (being adjusted to pH 3.8 with phosphoric acid) is by means of magnetic drive pump recirculated through non-cellular-type filters pressing electrolytic cell, the non-cellular-type
Filters pressing electrolytic cell is by yttrium oxide base DSA anode (20cm2) and 20cm2(geometric area)GDL-24BC cathode (passes through
PP separator is spaced each other 0.8cm) composition.Apply voltage between the anode and cathode by using DC power supply to make electric current
(2A,1000A/m2) circulation.Electrolysis keeps 1.90h under room temperature (20-25 DEG C), the reason converted completely corresponding to 3-Hydroxybutanone
By the 102.8% of charge, it is assumed that current efficiency 100%.Initial soln pH is 3.8, final pH 3.7.After electrolysis, electricity
The methyl ethyl ketone for solving solution (57.8mL) 3-Hydroxybutanone containing 25.5g/L concentration and 41.7g/L concentration, such as HPLC institute
Show.Therefore, 3-Hydroxybutanone conversion ratio is 75.7% (73.6% current efficiency), and MEK yield is that 48.5% (MEK selectance is
64%), MEK productivity is 0.65kg MEK/h/m2。
Embodiment 26
Equally with embodiment 25 (comparative example), it but is replaced using lead plateGDL-24BC is as cathode.3-
Hydroxy butanone conversion ratio is 82.3% (80.1% current efficiency), and MEK yield is 62.1% (MEK selectance is 75.4%), MEK
Productivity is 0.83kg MEK/h/m2, the MEK productivity than obtaining in comparative example 1 is high by 27.7%.
Embodiment 27-31
Similar with embodiment 26, the display of these embodiments uses the superiority of the method for the present invention of non-separated electrolysis bath
Energy.By 3-hydroxy-2-butanone (200g/L) and KH2PO4The aqueous solution (60mL) (being adjusted to pH 5.5 with KOH) of (10 weight %) is by means of magnetic
Power pump is with the flow velocity of 2L/min recirculated through the room of non-cellular-type filters pressing electrolytic cell, and the non-cellular-type filters pressing electrolytic cell is by conduct
The Ti support type yttrium oxide base DSA sieve (20cm of anode2Geometric area) and as cathode lead plate (20cm2) composition.Electrode
Between gap be 0.8cm.Apply voltage between the anode and cathode by using DC power supply provide current cycle (in table 2
Current density, J (A/m2)).It is given in Table 2 with the charge Q that the % of theoretical charge is indicated, and temperature is 22 DEG C.As a result
It is given in Table 2.
Result in the non-separated electrolysis bath of table 2..The meaning met is as table 1.
Embodiment 32
Equally with embodiment 28 (table 2), but carbon steel (C:0.40-0.50% is used；Mn:0.50-0.80%；Si:
0.15-0.40%) anode replaces Ti support type yttrium oxide base DSA sieve.3-hydroxy-2-butanone conversion ratio is 68% (100% electric current effect
Rate), MEK yield is 50.2% (50.2% current efficiency), causes to be 73.8% to the selectance of MEK.
Embodiment 33 (comparative example)
With 9 (comparative example of embodiment；Table 1) equally, the difference is that catholyte includes 40mL 3-hydroxy-2-butanone (100g/
L)、KH2PO4The aqueous solution (being adjusted to pH5.5 with KOH) and 20mL of (5 weight %) are used for the diformazan from water phase continuous extraction MEK
Benzene.After electrolysis, the concentration of 3-hydroxy-2-butanone is 7.95g/L in the water phase (42mL) of catholyte, and the concentration of MEK is
18.75g/L, and the concentration of 3-hydroxy-2-butanone is 0g/L in catholyte organic phase (15mL), the concentration of MEK is 67.7g/L, such as
Shown in HPLC.Therefore, 3-hydroxy-2-butanone conversion ratio is 91.7% (91.7% current efficiency), and MEK yield is 55% (55% electric current effect
Rate), cause to be 60% to the selectance of MEK.Therefore, conversion ratio and the conversion ratio obtained in the case where extractant is not present
It is equal but high by 8.3% to the selectance of MEK.MEK productivity is 0.79kg MEK/h/m2, than the MEK productivity of embodiment 10
It is high by 8.8%.The comparative example shows the progress with electrolysis, and the good effect of MEK is continuously removed by liquid-liquid extraction.
Industrial applicibility
Above-described embodiment demonstrates the industrial applicibility and its advantage of the method for the present invention.It can be in room temperature and environmental pressure
Under in the electrochemistry in industry method for manufacturing organic matter common current density (, current density related to craft rate of production
Higher, productivity is higher, and condition is that the percentage that current efficiency is kept constant or it is reduced is lower than the increase by hundred of current density
Point ratio) under operate.In addition, it can work in separated electrolysis bath and non-separated electrolysis bath, in non-separated electrolysis bath
In 85.5% (referring to embodiment 30, table 2) is up to the selectance of MEK, or in separated electrolysis bath be up to 86.7% (referring to
Embodiment 26, table 1), and MEK productivity is suitable for industrial production.
The bibliography of the application reference
1.US4075128
2.US5506363
3.Zhao etc., " Catalytic dehydration of 2,3-butanediol over P/HZSM-5:
effect of catalyst,reaction temperature and reactant configuration on
rearrangement products”,RSC Adv.,2016,Vol.14,pp.16988-16995.
4.WO2016097122
5.US3247085
6.Baizer etc., " Electrochemical conversion of 2,3-butanediol to 2-
butanone in undivided flow cells:a paired synthesis",J.Appl.Electrochem,1987,
Vol.14,pp.197-208
7.ES2352633
8.Popp FD and Schultz HP"Electrolytic reduction of organic compounds"
Electrolytic Reduction of Organic Compounds.Chem Rev,1962,Vol.62,pp:19-40
Claims (15)
1. it is a kind of by using the cathode being made by lead in an aqueous medium electroreduction 3-hydroxy-2-butanone and prepare methyl ethyl ketone (MEK)
Method, the described method comprises the following steps:
A) solution is formed and soluble supporting electrolyte mixes by 3-hydroxy-2-butanone with aqueous medium and in such medium, and
B) by using DC power supply with 500 to 5000A/m2Current density apply voltage between anode and the cathode,
The solution is continuously or non-continuously electrolysed in electrochemical reactor.
2. method as claimed in claim 1, wherein the reaction is carried out in the case where hydrogenation catalyst is not present, the hydrogenation is urged
Agent is can be catalyzed the group for being easy to be reduced in ontology catholyte by the catalyst of hydrogen reduction.
3. method as claimed in claim 2, wherein the hydrogenation catalyst is selected from by carried noble metal, thunder Buddhist nun Ni and support type Ni
The group of composition.
4. method according to any one of claims 1 to 3, wherein the cathode material is flat lead, or deposition
Lead in porous carrier, the porous carrier are, for example, carbon felt and carbon foam.
5. method according to any one of claims 1 to 4, wherein the anode is selected from: carbon steel, the platinum being supported on titanium and
The anode of iridium base dimensionally stable for non-porous flat form and is perforated material, for example, net, metallic screen, thin slice, forming net and
Grid.
6. the method as described in any one of claims 1 to 5, wherein the aqueous medium include 100 weight % water or
The mixture of water and complete or partial water miscibility electrically inactive solvent, in the mixture, the amount of water be 50 weight % extremely
99 weight %, especially 70 weight % are to 99 weight %, more particularly 85 weight % to 99 weight %.
7. such as method described in any one of claims 1 to 6, wherein the electrochemical reactor is non-cellular-type reactor.
8. the method as described in any one of claims 1 to 7, wherein the supporting electrolyte for forming solution with 3-hydroxy-2-butanone is selected from packet
Containing following groups: the ammonium salt and alkali and alkaline earth metal ions salt and quaternary ammonium salt of inorganic acid and its mixture, and for dividing
Every the supporting electrolyte of the anolyte in formula electrolytic cell be non-oxidizable inorganic acid.
9. method according to claim 8, wherein the gross mass based on the solution, forms the branch of solution with 3-hydroxy-2-butanone
The amount of electrolyte is held as 0.1 weight % to 20 weight %, especially 1 weight % to 15 weight %, more particularly 5 weight % to 10
Weight %.
10. method as claimed in any one of claims 1-9 wherein, wherein by by 3-hydroxy-2-butanone with aqueous medium and such
Soluble supporting electrolyte mixing in medium and the pH of solution formed are 2.5 to 7, especially 3 to 7, more particularly 4 to 7.
11. the method as described in any one of claims 1 to 10, it is assumed that current efficiency 100% is used for 3-hydroxy-2-butanone electricity also
Originally be MEK and the amount of electric power that recycles be for obtaining the theoretical amount of 100% 3-hydroxy-2-butanone conversion ratio 50% to 125%, more
Especially 55% to 100%, most particularly 60% to 75%.
12. the method as described in any one of claims 1 to 11, wherein electrolysis temperature is 10 DEG C to 70 DEG C, especially room temperature.
13. the method as described in any one of claims 1 to 12, wherein the MEK is by being evaporated in vacuo from described aqueous
It is continuously removed in medium.
14. the method as described in any one of claims 1 to 12, wherein MEK obtained is by using water-insoluble inertia
The liquid-liquid extraction of solvent and continuously removed from the aqueous medium.
15. the method as described in any one of claims 1 to 14 carries out in following reactors:
I) electrochemical reactor；Or
Ii) at least two electrochemical reactor being connected in series, what which to be generated by electrochemical reactor
Solution is supplied to subsequent electrochemical reactor, which includes unreacted 3-hydroxy-2-butanone, MEK, aqueous medium and in such medium
In soluble supporting electrolyte mixture.
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| EP16382424.6 | 2016-09-14 | ||
| EP16382424 | 2016-09-14 | ||
| PCT/EP2017/073021 WO2018050695A1 (en) | 2016-09-14 | 2017-09-13 | Electrochemical method for manufacturing methyl ethyl ketone |
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|---|---|
| US (1) | US20190194814A1 (en) |
| EP (1) | EP3512982B1 (en) |
| CN (1) | CN109790630B (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919349A (en) * | 1996-05-23 | 1999-07-06 | Basf Aktiengesellschaft | Electrochemical reduction of organic compounds |
| CN104313635A (en) * | 2014-10-31 | 2015-01-28 | 北京工业大学 | Electrochemical catalytic synthesis method of alpha-carbonyl ketone compounds |
| WO2016097122A1 (en) * | 2014-12-18 | 2016-06-23 | Fundacion Tecnalia Research & Innovation | Method for manufacturing 2,3-butanediol |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3247085A (en) | 1963-06-14 | 1966-04-19 | Exxon Research Engineering Co | Electrochemical process for making methyl-ethyl ketone |
| US4075128A (en) | 1976-11-26 | 1978-02-21 | Atlantic Richfield Company | Preparation of methyl ethyl ketone |
| CA2077552A1 (en) | 1990-03-05 | 1991-09-06 | John H. Grate | Catalytic system for olefin oxidation to carbonyl products |
| ES2352633B8 (en) | 2009-08-04 | 2012-02-20 | Fundacion Leia Centro De Desarrollo Tecnologico | MUTANT strain of LACTOCOCCUS LACTIS LACTIS AND METHOD FOR INDUSTRIAL PRODUCTION OF ACETOINE. |
| WO2013134220A1 (en) * | 2012-03-06 | 2013-09-12 | Board Of Trustees Of Michigan State University | Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds |
| CN104937015B (en) * | 2012-11-20 | 2020-03-17 | 卡比欧斯公司 | Method for recycling plastic articles |
-
2017
- 2017-09-13 US US16/329,428 patent/US20190194814A1/en not_active Abandoned
- 2017-09-13 EP EP17764416.8A patent/EP3512982B1/en active Active
- 2017-09-13 WO PCT/EP2017/073021 patent/WO2018050695A1/en unknown
- 2017-09-13 ES ES17764416T patent/ES2813570T3/en active Active
- 2017-09-13 CN CN201780055234.8A patent/CN109790630B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919349A (en) * | 1996-05-23 | 1999-07-06 | Basf Aktiengesellschaft | Electrochemical reduction of organic compounds |
| CN104313635A (en) * | 2014-10-31 | 2015-01-28 | 北京工业大学 | Electrochemical catalytic synthesis method of alpha-carbonyl ketone compounds |
| WO2016097122A1 (en) * | 2014-12-18 | 2016-06-23 | Fundacion Tecnalia Research & Innovation | Method for manufacturing 2,3-butanediol |
Non-Patent Citations (1)
| Title |
|---|
| M. M. BAIZER ET. AL.: "Electrochemical conversion of 2,3-butanediol to 2-butanone in undivided flow cells: a paired synthesis", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》 * |
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| US20190194814A1 (en) | 2019-06-27 |
| EP3512982B1 (en) | 2020-06-17 |
| EP3512982A1 (en) | 2019-07-24 |
| ES2813570T3 (en) | 2021-03-24 |
| CN109790630B (en) | 2021-05-25 |
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