CN110511127A - A method of alpha-alcohol ketone is prepared using ethynylation by-product - Google Patents
A method of alpha-alcohol ketone is prepared using ethynylation by-product Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
Abstract
The present invention provides a kind of method for preparing alpha-alcohol ketone using ethynylation by-product, use ethynylation by-product for raw material, using load type metal ruthenium as catalyst, make the acetylenic diols substance in raw material that Meyer-Schueter rearrangement reaction occur, alpha-alcohol ketone is obtained, selectivity of product is high, comprehensively utilizes ethynylation by-product, value of the product is improved, industrialized production is adapted to and needs.
Description
Technical field
The present invention relates to a kind of methods for preparing alpha-alcohol ketone using ethynylation by-product, and in particular to uses acetylene
Changing reaction to prepare the by-product acetylenic diols substance of alkynol is raw material, the method for preparing alpha-alcohol ketone.
Background technique
Ethynylation prepare alkynol be obtained in fine chemistry industry production organic intermediate and its chemical products method it
One, production VE, DV chrysanthemumic acid (pyrethroids intermediate), vitamin A, vitamin K1, carotenoid intermediate, synthetic rubber monomer and
The products such as fragrance are directed to ethynylation.
Ethynylation selectivity is higher, and main side reaction is the dimerisation products that the secondary ethynylation of raw material is formed, such as with
During methyl heptenone prepares dehydrolinalool, main by-product is dimerization dehydrolinalool.Usual ethinylation crude product
Middle dimerisation products mass content is not higher than 5%, but crude product, after rectifying or distillation processing, dimerisation products are by constantly dense in tower reactor
Contracting content is continuously improved, it might even be possible to up to 90% or more.Tower bottoms is in furvous, and viscosity is larger, is not directly arranged to environment
It puts, it usually needs burning disposal.This not only causes the waste of resource, also brings adverse effect to environmental protection.
A kind of side by dehydrogenated linalool production waste liquor manufacture methyl heptenone is reported in patent CN200610118590
Method, principle are the reaction raw materials methyl heptenones for converting dimerisation products to by the back reaction of ethinylation ethinylation, are a kind of
Utilize the method for dimerisation products.But dimerisation products structure is special, resets to obtain product alpha-alcohol ketone by Meyer-Schueter
Substance can greatly improve its value.
Alpha-alcohol ketone is the organic molecule skeleton important for one kind, is widely present in a variety of with active point of important biomolecule
In son, synthetic drug and natural products.Alpha-alcohol ketone structure is special, has multiple reaction sites, and chemical property is active, can be with
It is reacted with a variety of nucleophilics or electrophilic reagent and forms new carbon-carbon bond, carbon-oxygen bond；And the condition of reaction is milder, operates phase
It to simple, thus is the important intermediate for constructing macromolecular and some important compounds (such as amino alcohol, glycol), Alpha-hydroxy assimilation
It is a kind of very important using very extensive photocuring photoinitiator for closing object.In addition, alpha-hydroxyacetone compounds are lured in chirality
Leading synthesis aspect also has application abundant.
Meyer-Schueter rearrangement reaction occurs under the catalysis of acid for propargyl alcohol class compound, is synthesis α, β-unsaturation
Carbonyls-kind of effective ways.This method has the characteristics that Atom economy is high, meets the requirement of Green Chemistry.Document
The mechanism of the Meyer-Schueter rearrangement,The Journal of Organic
Chemistry, 1977,42:3403-3408. report its mechanism etc..Document Explorations on the Total
Synthesis of the Unusual Marine Alkaloid Chartelline A,The Journal of Organic
Chemistry, 2006,71:3159-3166. and The Meyer-Schueter rearrangement for the
Synthesis of α,β-unsaturated carbonyl compounds.Organic&Biomolecular
There is the relevant report of such reaction in Chemistry, 2009,7:4149-4158..
Ethynylation by-product is used to be for the difficult point of reaction raw materials at present, after raw material is present in rectifying or distillation
In tower reactor, residual solution complicated component, impurity and heavy constituent all can service life to catalyst and catalytic selectivity have an impact, difficulty
Greatly.In addition molecular weight product is big, product purification difficult, it is desirable that high conversion and highly selective.
Summary of the invention
The present invention in order to solve the above technical problems, provides a kind of side that alpha-alcohol ketone is prepared using ethynylation by-product
Method, to realize following goal of the invention:
1, Meyer-Schueter rearrangement reaction is carried out by catalyst of load type metal ruthenium, high conversion obtains Alpha-hydroxy
Ketone.In addition it selects suitable modifying agent to adjust catalyst system, improves alpha-alcohol ketone selectivity.
2, catalyst stabilization, product component are stablized, alpha-alcohol ketone selectivity >=95.0%, easy to operate.
To achieve the above object, the invention adopts the following technical scheme:
Meyer- is carried out by catalyst of modified load type metal ruthenium after raw material, that is, acetylenic diols substance is purified
Schueter rearrangement reaction, high conversion highly selective obtain alpha-alcohol ketone.
The present invention provides a kind of method for preparing alpha-alcohol ketone using ethynylation by-product, using ethynylation pair
Product is raw material, using load type metal ruthenium as catalyst, makes the acetylenic diols substance in raw material that Meyer-Schueter weight occur
Row's reaction, obtains alpha-alcohol ketone.
In the present invention, require the polymeric impurities mass percentage for including low in the raw material ethynylation by-product
In 0.1%, the polymeric impurities include the impurity that molecular weight is higher than acetylenic diols substance, mainly by ethynylation system
The double bond contained and three key polymerizations generate.
In the present invention, in the ethynylation by-product include acetylenic diols substance, mass percentage be 30~
99%, preferably 60~99%.
In production process, the acetylenic diols substance of the high concentration of ethynylation by-product is primarily present at rectifying or distillation
In tower bottoms after reason, the mass concentration of acetylenic diols substance is between 30% to 95% in tower bottoms；The material is usually brown
Color thick liquid, when being directly used in Meyer-Schueter rearrangement reaction, polymer therein can make catalyst inactivation, therefore,
When the polymeric impurities content for including in ethynylation by-product is higher, such as in 0.1wt% or more, need to ethinylation
Byproduct of reaction is pre-processed, and the polymer in ethynylation by-product, pretreated acetylenic diols substance matter are removed
Percentage composition is measured usually between 60~99%, polymeric impurities content is lower than 0.1%.
In some specific embodiments of the present invention, raw material ethynylation by-product is including removing ethinylation before
The pretreatment operation of polymer in byproduct of reaction.The pretreatment preferably uses the modes such as distillation or rectifying, be such as evaporated under reduced pressure,
Rectification under vacuum or steam distillation etc..Ethynylation by-product in tower bottoms purifies acetylenic diols substance by pretreatment
And the component that boiling point is higher than acetylenic diols substance is removed, acetylenic diols material mass percentage composition is obtained between 60~99%
Raw material.
In the present invention, the ethynylation by-product, be with structure shown in formula I ketone or aldehyde compound by ethinylation
Reaction, the obtained by-product comprising the acetylenic diols substance with II structure of formula；
Wherein, R1、R2It is separately hydrogen or alkyl, and R1、R2It is not simultaneously hydrogen, the C1- of preferred branched or straight chain
C20 alkyl or alkenyl.
Further, the ketone compound includes but is not limited to acetone, 6- methyl -5- hepten-2-one, 6- methyl -2- heptan
Ketone, geranyl acetone, tetrahydrogeranylacetone, plant ketone etc., corresponding structural formula is as follows:
The acetylenic diols substance for including in corresponding obtained by-product are as follows: acetone acetylenic glycols, 6- methyl -5- hepten-2-one
Acetylenic glycols, geranyl acetone acetylenic glycols, tetrahydrogeranylacetone acetylenic glycols, plant ketone acetylenic glycols at 6- methyl -2-HEPTANONE acetylenic glycols
Deng structural formula is as follows:
In the present invention, the acetylenic diols substance with II structure of formula for including in above-mentioned by-product is through Meyer-Schueter
The alpha-alcohol ketone that rearrangement reaction obtains, structure is as shown in formula III:
Wherein, R1、R2With the R in formula I, II structure of formula1、R2It is identical.
Further, the alpha-alcohol ketone include but is not limited to acetone hydroxy-ketone, 6- methyl -5- hepten-2-one hydroxy-ketone,
6- methyl -2-HEPTANONE hydroxy-ketone, geranyl acetone hydroxy-ketone, tetrahydrogeranylacetone hydroxy-ketone, plant ketone hydroxy-ketone etc., correspond to
Structural formula it is as follows:
In the present invention, the load type metal ruthenium catalyst, wherein metal Ru mass percentage is 0.1~20%.
The load type metal ruthenium catalyst, composition include metal Ru, carrier and modifying agent.
The metal Ru, ruthenium source are selected from one of inorganic ruthenium compound or organic ruthenium compound or a variety of, preferably such as
One of ruthenium halide, nitric acid ruthenium, acetic acid ruthenium, acetylacetone,2,4-pentanedione ruthenium are a variety of.
The carrier is selected from one of inert metal oxides or inert inorganic carbon material or a variety of, preferably such as titanium dioxide
One of zirconium, titanium dioxide, silica, active carbon are a variety of.
The modifying agent is selected from third and fourth period metallic element, be one of metallic element simple substance or its compound or
It is a variety of, the metallic element preferably such as one of aluminium, zinc, copper, iron, cobalt, nickel, manganese or a variety of, in some embodiments of the invention
In, metallic element combination such as zinc and aluminium, cobalt, nickel and aluminium, copper and iron etc. that modifying agent uses；
The modifying agent, source metal is selected from one of soluble-salt of modifier metal element or a variety of, described to change
The soluble-salt of property agent metallic element is preferably one of zinc acetate, aluminum nitrate, ferric sulfate, cobalt chloride etc. or a variety of.
The modifying agent is to pass through the soluble-salt for adding above-mentioned modifier metal element in catalyst preparation process,
Then it is introduced using potassium borohydride or sodium borohydride reduction.The modifying agent is in load type metal ruthenium catalyst product
Existence form includes metallic element simple substance or its compound, metallic element simple substance, that is, metal reduction-state, and metallic element compound is
The soluble-salt of metallic element, wherein mainly existing in the form of metal reduction-state.The soluble-salt of metallic element is preparation process
Residual after the reduction of modifier metal source, different metal element is reduced ratio difference, as Zn-ef ficiency is only reduced on a small quantity
Simple substance, ferro element is then largely reduced to+2 valence or elemental.It, can in the presence of in the form of the soluble-salt by metallic element
The anion species of soluble also have an impact to catalytic effect, and anion species are different, and the catalytic effect of catalyst is also different.It deposits
The soluble-salt of the metallic element described in form is preferably such as one of zinc acetate, aluminum nitrate, ferric sulfate, cobalt chloride or more
Kind.
In the load type metal ruthenium catalyst, modifying agent additive amount in terms of metallic atom number in modifying agent, mole with
Amount is 0.5~50%, preferably the 1~10% of metal Ru molal quantity.
In the present invention, the load type metal ruthenium catalyst the preparation method comprises the following steps: firstly, by ruthenium source, modifier metal member
The soluble-salt of element, solvent mixing, are then added carrier, it is stirred 0.1~for 24 hours, after preferably 0.5~12h, it is dense that quality is added dropwise
The potassium borohydride or sodium borohydride aqueous solution of degree 1~15%, time for adding 0.1~for 24 hours, preferably 0.5~12h is added dropwise subsequent
Continuous stirring 0.1~2h of reduction reaction, most obtains catalyst through washing afterwards.
In the preparation method of the load type metal ruthenium catalyst, for guarantee catalyst catalytic performance, potassium borohydride or
The titration end-point pH of person's sodium borohydride aqueous solution is between 3 to 8.
In the preparation method of the load type metal ruthenium catalyst, solvent be selected from pure water, do not react with raw material it is lazy
One of property aliphatic alkane, aromatic hydrocarbons, ethers, alcohols are a variety of, for example, one of pure water, normal heptane, toluene, ethyl alcohol or
It is a variety of, preferred pure water.In some embodiments of the present invention, before catalyst preparation, the soluble-salt of modifier metal element or
The available solvent dissolution in ruthenium source, both solvents can be used same solvent or different solvents dissolution, dissolve modifier metal element
Soluble-salt when solution mass concentration be chosen as 0.1~5%.
In the preparation method of the load type metal ruthenium catalyst, the soluble-salt in the ruthenium source and modifier metal element
Mass ratio is 0.5~50:1, preferably 2~10:1.
The solvent usage is 20~100 times of ruthenium source quality.
The molar ratio in the potassium borohydride or sodium borohydride and ruthenium source is 0.5~2:1.
In the present invention, the raw material, that is, ethynylation by-product (include acetylenic diols substance) can be diluted or not with solvent
Using solvent, solvent is selected from one of pure water, the inert aliphatic race alkane not reacted with raw material, aromatic hydrocarbons, ethers, alcohols
Or it is a variety of, such as one of pure water, normal heptane, toluene, ethyl alcohol or a variety of；Preferably, the dosage of dilution solvent is acetylene
0.1~3.0 times, preferably 0.2~1.0 times for changing byproduct of reaction quality.
In the present invention, the Meyer-Schueter rearrangement reaction can carry out under atmosphere of inert gases, inertia used
Gas can be selected from nitrogen, argon gas etc..Preferably, the inert gas volumetric concentration should be 99.9% or more.
In the present invention, the load type metal ruthenium catalyst dosage is the 0.5~5% of ethynylation by-product amount of substance.
The Meyer-Schueter rearrangement reaction, reaction temperature are 0~180 DEG C, preferably 20~120 DEG C；Reaction time
0.5~for 24 hours, preferably 2~8h.
It is of the present invention to be prepared in the method for alpha-alcohol ketone using ethynylation by-product, acetylenic diols substance conversion ratio
>=95.0%, alpha-alcohol ketone selectivity >=95.0%.Every gram of load type metal ruthenium catalyst completes 2000 grams of alkynes in the present invention
Activity is not decreased obviously after two alcohol catalysis.
The present invention uses ethynylation by-product for raw material, and raw material is present in the tower reactor after rectifying or distillation, due to
Residual solution complicated component, impurity and heavy constituent all can service life to catalyst and catalytic selectivity have an impact, conversion ratio and choosing
It is big that selecting property improves difficulty.Transition metal-catalyzed organic reaction is to realize that the high chemo-selective of organic synthesis, high yield have
Effect approach, while its mild condition is easy, also complies with the requirement of atom economy sexual development.Due in transition metal containing not by
The track being full of, therefore it can not only receive electronics, but also can provide electronics, these characteristics play particularly important in catalysis
Effect.Ruthenium catalyst has important application in isomerization, and especially ruthenium is in the special ability of activation end triple carbon-carbon bonds
Rearrangement reaction provides new thinking.
The positive effect of the present invention is: firstly, the raffinate originally as liquid waste processing is made full use of, economic value is obtained
To promotion, environmental protection pressure is reduced.Secondly, by adding suitable modifying agent in system, it will be able to realize high conversion, Gao Xuan
Selecting property obtains alpha-alcohol ketone.Finally, catalyst system efficient stable, product component is stablized, suitable actual production easy to operate.
Specific embodiment
The following examples will be further described technique provided by the present invention, but the present invention is not limited to listed
Embodiment out should also include other any well known changes in interest field of the presently claimed invention.
One, embodiment primary raw material source:
Tower bottoms after 6- methyl -5- hepten-2-one ethynylation, with 6- methyl -5- heptan of Beijing Yi Nuokai Science and Technology Ltd.
Alkene -2- ketone is that raw material rectifying removing dehydrogenation linalool after ethynylation obtains.The material is brown thick liquid, composition are as follows: w
(dehydrogenation linalool)=22.8%, w (6- methyl -5- hepten-2-one acetylenic glycols)=57.9%, other predominantly polymer are miscellaneous
Matter；
Tower bottoms after geranyl acetone ethynylation is passed through by raw material of the geranyl acetone of Hangzhou Yu Hao Chemical Industry Science Co., Ltd
Rectifying removes dehydrogenation linalool and obtains after ethynylation.The material is brown thick liquid, composition are as follows: w (dehydrogenation nerolidol)
=15.6%, w (geranyl acetone acetylenic glycols)=68.7%, other predominantly polymeric impurities；
Ruthenic chloride, 99w%, Xin Nuoke Science and Technology Ltd.；
Zinc sulfate, 99w%, lark prestige Science and Technology Ltd.；
Aluminum nitrate, 99w%, lark prestige Science and Technology Ltd..
Two, analysis instrument and method:
Gas chromatograph: Agilent7820A, chromatographic column HP-5 (0.25 μm of the μ m of 30m × 320), injector temperature: 150
℃；Split ratio 50:1；Carrier gas flux: 1.5ml/min；Temperature program: 40 DEG C of holding 1min are warming up to 90 DEG C with 10 DEG C/min,
0min is kept, is then warming up to 160 DEG C with 5 DEG C/min, keeps 0min, is then warming up to 280 DEG C with 30 DEG C/min, is kept
6min.Detector temperature: 280 DEG C.
1 pretreatment of raw material 1 of embodiment
Tower bottoms 1000g after 6- methyl -5- hepten-2-one ethynylation is taken to carry out vacuum distillation processing, tower bottoms composition are as follows: w
(dehydrogenation linalool)=22.8%, w (6- methyl -5- hepten-2-one acetylenic glycols)=57.9%, other predominantly polymer are miscellaneous
Matter.Vacuum distillation vacuum degree is 200Pa (absolute pressure), and 180 DEG C of bottom temperature, the dehydrogenation virtue camphor tree that purity is 98.4% is obtained in tower top
Alcohol 226g.Vacuum degree is adjusted to 100Pa, 260 DEG C of bottom temperature, the 6- methyl -5- heptene-that purity is 98.2% is obtained in tower top
2- ketone acetylenic glycols 575g, wherein dehydrogenation linalool content is 0.94%, and polymeric impurities content is lower than 1ppm (being not detected).Tower top
Obtained material is by-product after pretreatment.
2 pretreatment of raw material 2 of embodiment
Tower bottoms 1000g after geranyl acetone ethynylation is taken to carry out vacuum distillation processing, tower bottoms composition are as follows: w (dehydrogenation flores aurantii
The tertiary alcohol)=15.6%, w (geranyl acetone acetylenic glycols)=68.7%, other predominantly polymeric impurities.It is evaporated under reduced pressure vacuum degree
For 200Pa (absolute pressure), 210 DEG C of bottom temperature, the dehydrogenation linalool 157g that purity is 98.3% is obtained in tower top.By vacuum degree tune
To 100Pa, 280 DEG C of bottom temperature, the geranyl acetone acetylenic glycols 575g that purity is 98.5% is obtained in tower top, wherein dehydrogenation orange
Flower tertiary alcohol content is 0.33%, polymeric impurities content 0.01%.The material that tower top obtains is by-product after pretreatment.
The preparation of 3 load type metal ruthenium catalyst I of embodiment
I preparation process of catalyst is as follows: weigh 1.0g ruthenium trichloride solid and 0.1g zinc sulfate (as zinc modification agent),
0.1g aluminum nitrate (aluminium modifying agent) is dissolved in 50g pure water, is stirred 60min, is allowed to sufficiently dissolve.5.0g zirconium dioxide is added to make
For carrier, 60min is stirred, is allowed to be sufficiently mixed.5% potassium borohydride aqueous solution of mass concentration is added dropwise, is allowed to restore.With boron hydrogen
Change the dropwise addition of potassium solution, the pH value of reaction system changes, when pH value stops being added dropwise by rising to lower than 2 when pH is 4, when dropwise addition
Between 0.5h, continue stir reduction reaction 60min.Load type metal ruthenium catalyst I is obtained after pure water 10 times, for use.
In load type metal ruthenium catalyst I obtained metal Ru mass percentage be 9.76%, modifying agent additive amount with
Zinc and aluminium element and meter, mole are the 18.38% of metal Ru molal quantity.
The preparation of 4 load type metal ruthenium catalyst II of embodiment
Catalyst II preparation process is as follows: weigh 1.0g nitric acid ruthenium solid and 0.1g cobaltous sulfate (as cobalt improved dose),
0.1g nickel nitrate (nickel modifying agent), 0.1g aluminium chloride (aluminium modifying agent) are dissolved in 100g pure water, are stirred 120min, are allowed to abundant
Dissolution.10.0g titanium dioxide is added as carrier, stirs 120min, is allowed to be sufficiently mixed.8% hydroboration of mass concentration is added dropwise
Aqueous solutions of potassium is allowed to restore.With the dropwise addition of solution of potassium borohydride, the pH value of reaction system changes, when pH value is by being lower than 2
It rises to and stops being added dropwise when pH is 6, time for adding 1h continues to stir reduction reaction 120min.It must be loaded after pure water 10 times
Type metal Ru catalyst II, for use.
In load type metal ruthenium catalyst II obtained metal Ru mass percentage be 3.63%, modifying agent additive amount with
Cobalt, nickel and aluminium element and meter, mole are the 45.95% of metal Ru molal quantity.
The preparation of 5 load type metal ruthenium catalyst III of embodiment
III preparation process of catalyst is as follows: the copper sulphate for weighing 1.0g acetic acid acid ruthenium solid and 0.05g is (modified as copper
Agent), 0.05g iron chloride (iron modifying agent) be dissolved in 40g pure water, stir 90min, be allowed to sufficiently dissolve.10.0g activity is added
Charcoal stirs 90min, is allowed to be sufficiently mixed as carrier.8% solution of potassium borohydride of mass concentration is added dropwise, is allowed to restore.With boron
The dropwise addition of aqueous solutions of potassium is hydrogenated, the pH value of reaction system changes, when pH value stops dropwise addition, drop by rising to lower than 2 when pH is 8
1.5h between added-time continues to stir reduction reaction 90min.Load type metal ruthenium catalyst III is obtained after pure water 10 times, for use.
In load type metal ruthenium catalyst III obtained metal Ru mass percentage be 3.63%, modifying agent additive amount with
Copper and ferro element and meter, mole are the 17.32% of metal Ru molal quantity.
Embodiment 6
6- methyl -5- the heptene-for being first 98.2% to purity after ethyl alcohol 100g is added in autoclave, embodiment 1 pre-processes
2- ketone acetylenic glycols 100g, 1.0g load type metal ruthenium catalyst I, autoclave is sealed.Use 0.5MPa (gauge pressure) nitrogen displacement 6
It is secondary, agitating paddle is opened, reaction kettle is kept internal temperature at into 90 DEG C of reaction 5h.Stop release after stirring and cooling down.It is filtered to remove catalysis
Agent takes a small amount of liquid to be analyzed, gas chromatographic analysis product composition.Reaction solution composition: 6- methyl -5- hepten-2-one hydroxyl
Ketone 95.6%, 6- methyl -5- hepten-2-one acetylenic glycols 1.3%, other 3.1%.Conversion ratio 98.68%, selectivity 98.66%.
Embodiment 7
6- methyl -5- heptene-the 2- for being first 98.2% to purity after ethyl alcohol 50g is added in autoclave, embodiment 1 pre-processes
Ketone acetylenic glycols 100g, 1.0g load type metal ruthenium catalyst II, autoclave is sealed.Use 0.5MPa (gauge pressure) nitrogen displacement 6
It is secondary, agitating paddle is opened, reaction kettle is kept internal temperature at into 120 DEG C of reaction 2h.Stop release after stirring and cooling down.It is filtered to remove catalysis
Agent takes a small amount of liquid to be analyzed, gas chromatographic analysis product composition.Reaction solution composition: 6- methyl -5- hepten-2-one hydroxyl
Ketone 96.3%, 6- methyl -5- hepten-2-one acetylenic glycols 0.8%, other 2.9%.Conversion ratio 99.19%, selectivity 98.87%.
Embodiment 8
6- methyl -5- heptene-the 2- for being first 98.2% to purity after ethyl alcohol 20g is added in autoclave, embodiment 1 pre-processes
Ketone acetylenic glycols 20g, 1.0g load type metal ruthenium catalyst I, autoclave is sealed.It is replaced 6 times using 0.5MPa (gauge pressure) nitrogen,
Agitating paddle is opened, reaction kettle is kept internal temperature at into 30 DEG C of reactions for 24 hours.Stop release after stirring and cooling down.Filtration of catalyst,
A small amount of liquid is taken to be analyzed, gas chromatographic analysis product composition.Reaction solution composition: 6- methyl -5- hepten-2-one hydroxy-ketone
91.8%, 6- methyl -5- hepten-2-one acetylenic glycols 5.8%, other 2.4%.Conversion ratio 94.09%, selectivity 99.35%.
Embodiment 9
The geranyl acetone acetylenic glycols for being first 98.5% to purity after ethyl alcohol 40g is added in autoclave, embodiment 2 pre-processes
200g, 1.0g load type metal ruthenium catalyst III, autoclave is sealed.It is replaced 6 times using 0.5MPa (gauge pressure) nitrogen, unlatching is stirred
Paddle is mixed, reaction kettle is kept internal temperature at into 110 DEG C of reaction 2h.Stop release after stirring and cooling down.Filtration of catalyst takes a small amount of
Liquid is analyzed, gas chromatographic analysis product composition.Reaction solution composition: geranyl acetone hydroxy-ketone 95.2%, geranyl third
Ketone acetylenic glycols 2.2%, other 2.6%.Conversion ratio 97.77%, selectivity 98.86%.
Embodiment 10
The geranyl acetone alkynes two for being first 98.5% to purity after ethyl alcohol 100g is added in autoclave, embodiment 2 pre-processes
Alcohol 100g, 1.0g load type metal ruthenium catalyst II, autoclave is sealed.It is replaced 6 times, is opened using 0.5MPa (gauge pressure) nitrogen
Reaction kettle is kept internal temperature at 60 DEG C of reaction 8h by agitating paddle.Stop release after stirring and cooling down.Filtration of catalyst takes few
Quantity of fluid is analyzed, gas chromatographic analysis product composition.Reaction solution composition: geranyl acetone hydroxy-ketone 96.5%, geranyl
Acetone acetylenic glycols 1.3%, other 2.2%.Conversion ratio 98.68%, selectivity 99.28%.
Comparative example 1
IV preparation process of catalyst is as follows: the plumbi nitras for weighing 1.0g ruthenium trichloride solid and 0.1g is dissolved in 50g pure water
In, 60min or more is stirred, is allowed to sufficiently dissolve.5.0g zirconium dioxide is added as carrier, stirs 60min or more, is allowed to abundant
Mixing.5% solution of potassium borohydride of mass concentration is added dropwise, is allowed to restore.With the dropwise addition of solution of potassium borohydride, the pH of reaction system
Value changes, and stops being added dropwise when pH value reaches 4, continues to stir 60min.Catalyst is stand-by after pure water 10 times.
In load type metal ruthenium catalyst IV obtained metal Ru mass percentage be 9.76%, modifying agent additive amount with
Lead element meter, mole are the 6.23% of metal Ru molal quantity.
6- methyl -5- the heptene-for being first 98.2% to purity after ethyl alcohol 100g is added in autoclave, embodiment 1 pre-processes
2- ketone acetylenic glycols 100g, 1.0g metal Ru catalyst IV, autoclave is sealed.It is replaced 6 times, is opened using 0.5MPa (gauge pressure) nitrogen
Agitating paddle is opened, reaction kettle is kept internal temperature at into 90 DEG C of reaction 5h.Stop release after stirring and cooling down.Filtration of catalyst takes
A small amount of liquid is analyzed, gas chromatographic analysis product composition.Reaction solution composition: 6- methyl -5- hepten-2-one hydroxy-ketone
35.2%, 6- methyl -5- hepten-2-one acetylenic glycols 59.7%, other 5.1%.Conversion ratio 39.21%, selectivity 91.34%.
Comparative example 2
V preparation process of catalyst is as follows: weigh 1.0g ruthenium trichloride solid and be dissolved in 50g pure water, stir 60min with
On, it is allowed to sufficiently dissolve.5.0g zirconium dioxide is added as carrier, stirs 60min or more, is allowed to be sufficiently mixed.Quality is added dropwise
5% solution of potassium borohydride of concentration, is allowed to restore.With the dropwise addition of solution of potassium borohydride, the pH value of reaction system changes, when
PH value stops being added dropwise when reaching 4, continues to stir 60min.Catalyst is stand-by after pure water 10 times.Load type metal obtained
Metal Ru mass percentage is 9.76% in ruthenium catalyst V.
6- methyl -5- the heptene-for being first 98.2% to purity after ethyl alcohol 100g is added in autoclave, embodiment 1 pre-processes
2- ketone acetylenic glycols 100g, 1.0g metal Ru catalyst V, autoclave is sealed.It is replaced 6 times, is opened using 0.5MPa (gauge pressure) nitrogen
Agitating paddle is opened, reaction kettle is kept internal temperature at into 90 DEG C of reaction 5h.Stop release after stirring and cooling down.Filtration of catalyst takes
A small amount of liquid is analyzed, gas chromatographic analysis product composition.Reaction solution composition: 6- methyl -5- hepten-2-one hydroxy-ketone
76.9%, 6- methyl -5- hepten-2-one acetylenic glycols 11.7%, other 11.4%.Conversion ratio 88.09%, selectivity 88.90%.
Comparative example 3
Ethyl alcohol 100g, 1.0g load type metal ruthenium catalyst I, 6- methyl -5- hepten-2-one alkynes is added to autoclave first
Glycol 100g, 6- methyl -5- hepten-2-one acetylenic glycols composition: w (dehydrogenation linalool)=5.4%, w (6- methyl -5- heptene -2-
Ketone acetylenic glycols)=89.5%, other predominantly polymeric impurities；Autoclave is sealed.Use 0.5MPa (gauge pressure) nitrogen displacement 6
It is secondary, agitating paddle is opened, reaction kettle is kept internal temperature at into 90 DEG C of reaction 5h.Stop release after stirring and cooling down.It is filtered to remove catalysis
Agent takes a small amount of liquid to be analyzed, gas chromatographic analysis product composition.Reaction solution composition: 6- methyl -5- hepten-2-one alkynes two
Alcohol 89.3%, dehydrogenation linalool 5.4%, other 5.3%.
Claims (10)
1. a kind of method for preparing alpha-alcohol ketone using ethynylation by-product, which is characterized in that use ethynylation pair
Product is raw material, using load type metal ruthenium as catalyst, makes the acetylenic diols substance in raw material that Meyer-Schueter weight occur
Row's reaction, obtains alpha-alcohol ketone.
2. the method according to claim 1, wherein requiring the polymerization for including in the ethynylation by-product
Object impurity mass percentage is lower than 0.1%；And/or
In the ethynylation by-product include acetylenic diols substance, mass percentage be 30~99%, preferably 60~
99%；And/or
Ethynylation by-product is including pretreatment operation before, and the pretreatment preferably uses distillation or rectifying mode,
Such as vacuum distillation, rectification under vacuum or steam distillation.
3. method according to claim 1 or 2, which is characterized in that the ethynylation by-product is with formula I
The ketone or aldehyde compound of structure pass through ethynylation, the obtained by-product comprising the acetylenic diols substance with II structure of formula
Object；
Wherein, R1、R2It is separately hydrogen or alkyl, and R1、R2It is not simultaneously hydrogen, the C1-C20 alkyl of preferred branched or straight chain
Or alkenyl；
Preferably, the ketone compound includes but is not limited to acetone, 6- methyl -5- hepten-2-one, 6- methyl -2-HEPTANONE, spiceleaf
Benzylacetone, plants ketone at tetrahydrogeranylacetone；The acetylenic diols substance for including in corresponding obtained by-product be acetone acetylenic glycols,
6- methyl -5- hepten-2-one acetylenic glycols, 6- methyl -2-HEPTANONE acetylenic glycols, geranyl acetone acetylenic glycols, tetrahydrogeranylacetone
Acetylenic glycols plant ketone acetylenic glycols；And/or
The alpha-alcohol ketone, structure is as shown in formula III:
Wherein, R1、R2With the R in formula I, II structure of formula1、R2It is identical；
Preferably, the alpha-alcohol ketone includes but is not limited to acetone hydroxy-ketone, 6- methyl -5- hepten-2-one hydroxy-ketone, 6- first
Base -2-HEPTANONE hydroxy-ketone, tetrahydrogeranylacetone hydroxy-ketone, plants ketone hydroxy-ketone at geranyl acetone hydroxy-ketone.
4. method according to claim 1-3, which is characterized in that the load type metal ruthenium catalyst, wherein
Metal Ru mass percentage is 0.1~20%；
The load type metal ruthenium catalyst, composition include metal Ru, carrier and modifying agent；
The metal Ru, ruthenium source are selected from one of inorganic ruthenium compound or organic ruthenium compound or a variety of, preferably ruthenium halide,
One of nitric acid ruthenium, acetic acid ruthenium, acetylacetone,2,4-pentanedione ruthenium are a variety of；
The carrier is selected from one of inert metal oxides or inert inorganic carbon material or a variety of, preferably zirconium dioxide, two
One of titanium oxide, silica, active carbon are a variety of；
The modifying agent is selected from third and fourth period metallic element, is one of metallic element simple substance or its compound or a variety of,
One of the preferred aluminium of the metallic element, zinc, copper, iron, cobalt, nickel, manganese are a variety of；It is further preferred that modifying agent additive amount
In terms of metallic atom number in modifying agent, mole dosage is 0.5~50%, preferably the 1~10% of metal Ru molal quantity；
Preferably, the modifying agent, source metal is selected from one of soluble-salt of modifier metal element or a variety of, described
The soluble-salt of modifier metal element is preferably one of zinc acetate, aluminum nitrate, ferric sulfate, cobalt chloride or a variety of；
Preferably, the modifying agent is by the soluble-salt of addition modifier metal element in catalyst preparation process, so
It is introduced afterwards using potassium borohydride or sodium borohydride reduction.
5. method according to claim 1-4, which is characterized in that the preparation of the load type metal ruthenium catalyst
Method are as follows: firstly, ruthenium source, the soluble-salt of modifier metal element, solvent are mixed, carrier is then added, is stirred 0.1
~for 24 hours, after preferably 0.5~12h, the potassium borohydride or sodium borohydride aqueous solution of mass concentration 1~15%, time for adding is added dropwise
0.1~for 24 hours, preferably 0.5~12h continues to stir 0.1~2h of reduction reaction after dropwise addition, most obtains catalyst through washing afterwards；
Preferably, the titration end-point pH of potassium borohydride or sodium borohydride aqueous solution is 3~8.
6. method according to claim 1-5, which is characterized in that solvent occurs anti-selected from pure water, not with raw material
One of the inert aliphatic race alkane answered, aromatic hydrocarbons, ethers, alcohols are a variety of, such as in pure water, normal heptane, toluene, ethyl alcohol
It is one or more, preferred pure water.
7. method according to claim 1-6, which is characterized in that the preparation of the load type metal ruthenium catalyst
In method, the soluble-salt mass ratio of the ruthenium source and modifier metal element is 0.5~50:1, preferably 2~10:1；And/or
The solvent usage is 20~100 times of ruthenium source quality；And/or
The molar ratio in the potassium borohydride or sodium borohydride and ruthenium source is 0.5~2:1.
8. method according to claim 1-7, which is characterized in that the ethynylation by-product can use solvent
Dilution does not use solvent, inert aliphatic race alkane, aromatic hydrocarbons, the ethers, alcohols that solvent is selected from pure water, does not react with raw material
One of or a variety of, such as one of pure water, normal heptane, toluene, ethyl alcohol or a variety of；Preferably, the dosage of solvent is second
0.1~3.0 times of ethynylation by-product amount of substance, preferably 0.2~1.0 times.
9. method according to claim 1-8, which is characterized in that the Meyer-Schueter rearrangement reaction can
To carry out under atmosphere of inert gases, inert gas used is selected from nitrogen, argon gas；Preferably, the inert gas volumetric concentration
It should be 99.9% or more.
10. method according to claim 1 to 9, which is characterized in that the load type metal ruthenium catalyst is used
Amount is the 0.5~5% of ethynylation by-product amount of substance；And/or
The Meyer-Schueter rearrangement reaction, reaction temperature are 0~180 DEG C, preferably 20~120 DEG C；Reaction time 0.5~
For 24 hours, preferably 2~8h.
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| CN112409147A (en) * | 2020-11-18 | 2021-02-26 | 万华化学集团股份有限公司 | Method for preparing aldehyde or ketone by cracking acetylene still residual liquid |
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| CN112409147A (en) * | 2020-11-18 | 2021-02-26 | 万华化学集团股份有限公司 | Method for preparing aldehyde or ketone by cracking acetylene still residual liquid |
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