CN106117035B - A kind of method for lactic acid conversion to produce propionic acid - Google Patents

A kind of method for lactic acid conversion to produce propionic acid Download PDF

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CN106117035B
CN106117035B CN201610505057.6A CN201610505057A CN106117035B CN 106117035 B CN106117035 B CN 106117035B CN 201610505057 A CN201610505057 A CN 201610505057A CN 106117035 B CN106117035 B CN 106117035B
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lactic acid
propionic acid
reaction
reducing agent
catalyst
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CN106117035A (en
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霍志保
肖杰锋
任德章
金放鸣
姜乃萌
姚国栋
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Shenzhen Aigeli Biological Technology Co ltd
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Shanghai Jiao Tong University
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups

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Abstract

The invention discloses a kind of lactic acid to convert the method for producing propionic acid.The method comprises the following steps: lactic acid, catalyst, reducing agent and water are successively added into hydrothermal reactor;It is filled with nitrogen into above-mentioned hydrothermal reactor and seals;30~180min is reacted under the conditions of above-mentioned hydrothermal reactor is placed in 175~300 DEG C;After reaction, filtering is to get propionic acid solution.This method can be effectively synthesized propionic acid with high selectivity.The raw material that this method uses can derive from reproducible biomass energy, avoid the consumption of fossil energy, without the catalyst of synthesis complex and expensive, this method is easy to operate, high conversion rate, is not necessarily to pure hydrogen, is small using water as hydrogen source and reaction dissolvent environmental pollution, is conducive to industrialized production.

Description

A kind of method that lactic acid conversion produces propionic acid
Technical field
The present invention relates to field of energy and chemical technologys, and in particular to a kind of method that lactic acid conversion produces propionic acid, more specifically It is a kind of method for preparing propionic acid using biomass derivatives lactic acid.
Background technique
Since 21 century, the shortage problem of environmental pollution and fossil fuel is more and more prominent, develops as a result, new renewable Clean energy resource more and more paid close attention to by people with reducing dependence to fossil fuel.It is industrial wide both at home and abroad at present The propionic acid synthetic method of general application be based primarily upon consumption fossil energy commercial synthesis method, the technique mainly have it is unsustainable, set It is standby to require the disadvantages of high, severe reaction conditions and energy consumption are high.Non-renewable due to petroleum resources, reserves are inevitable increasingly withered It exhausts, therefore has been imperative using reproducible raw material production propionic acid.And biomass energy have reproducibility, low pollution, Widely distributed property and the abundant feature of total amount, there is very big application prospect.
Summary of the invention
The present invention provides a kind of method for preparing propionic acid based on biomass derivatives lactic acid (DL type), and this method is one The completely new method of kind.This method does solvent and hydrogen source with water, and low energy consumption, and environmental pollution is small, is conducive to industrialized production, and convert High-efficient, good product selectivity, catalyst is cheap and easy to get, easy to operate.Product propionic acid is as a kind of important chemical intermediate And solvent, it is the important source material of esterifying agent, the solvent of nitrocellulose, plasticizer, chemical reagent and synthetic food raw material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of method that lactic acid conversion produces propionic acid, the method are as follows: be added to the water lactic acid, catalyst, reducing agent, lazy Property atmosphere under carry out hydro-thermal reaction, reaction temperature is 175~300 DEG C, 30~180min of reaction time, in reaction solution i.e. Obtain propionic acid.
Preferably, the reaction system obtained after reaction is filtered to get propionic acid solution is arrived.
Preferably, the lactic acid, catalyst, reducing agent molar ratio be 1.5:(2~10): (5~25).
It is highly preferred that the molar ratio of the lactic acid, catalyst, reducing agent is 1.5:(4~6): (10~15).
Preferably, the reaction density of the lactic acid is 100~250mmol/L.
Preferably, the catalyst is selected from metal or metal oxide.It is highly preferred that the catalyst be selected from Co, Ni, Cu、Fe、Fe2O3、CuO、Cu2O、Ni2O3Or Fe3O4One kind.It is further preferred that the catalyst is Co.
Preferably, the reducing agent is metal simple-substance powder.It is highly preferred that the metal simple-substance is Al, Fe, Mn or Zn. It is further preferred that the metal simple-substance is Zn.
Preferably, the method that the lactic acid conversion produces propionic acid includes the following steps:
A, lactic acid, catalyst, reducing agent and water are sequentially added into hydrothermal reactor;
B, it is filled with nitrogen into above-mentioned hydrothermal reactor and seals;
C, 30~180min is reacted under the conditions of above-mentioned hydrothermal reactor being placed in 175~300 DEG C;
D, after reaction, filtering is to get propionic acid solution.
Preferably, the filling rate of water is 20~45% in the hydrothermal reactor.
The atmosphere of inert gases be in order to which air is sufficiently discharged, may be to reaction to avoid certain ingredients in air It influences.
Preferably, the hydrothermal reactor, which is placed in baking oven, is reacted.
Preferably, in step D, the filtering is specially to be filtered using 0.45 μm of filter membrane.
In the method for the invention, water reacts 30~180min in 175~300 DEG C under the conditions of in hydrothermal reactor High-temperature high pressure water;The dielectric constant of high-temperature high pressure water has reduction than normal-temperature water, and intermolecular hydrogen bond weakens, and isothermal compressibility mentions Height, ion constant (Kw) almost increase 1000 times than normal-temperature water.
The reaction process are as follows: the reducing agent is reacted with water generates in-situ hydrogen, and then the in-situ hydrogen and the cream Two step reduction reactions occur under the catalyst action for acid, so the present invention can be complete in the condition without being additionally passed through pure hydrogen At the synthesis of propionic acid.
In addition, specific example is as follows there is also some possible side reaction processes in the above process:
Preferably, the lactic acid is biomass derivatives lactic acid.Utilize one of the reaction of biomass derivatives lactic acid producing Example can be found in Y.Fang et al., Industrial&Engineering Chemistry Research, and 2012,51 (12):4759-4763。
Compared with prior art, the present invention have it is following the utility model has the advantages that
(1) high-temperature high pressure water is generated in reaction process of the present invention make reaction dissolvent, compared with light water, high-temperature high pressure water Dielectric constant reduces, and intermolecular hydrogen bond weakens, and isothermal compressibility improves, and ion constant (Kw) is almost increased than normal-temperature water 1000 times, using these characteristics of high-temperature high pressure water, it can be achieved that making reducing agent with metal and its compound cheap and easy to get and urging Lactic acid is transformed into this high added value organic matter of propionic acid under hydrothermal conditions by agent, realizes that efficient low-consume converts organic money Source;
(2) present invention utilizes water to production hydrogen in situ, avoids the storage transport of hydrogen, significantly reduces energy consumption of reaction, And it is more environmentally protective, environmental pollution is small;
(3) reducing agent and catalyst can be recovered or make other production purposes in the method for the present invention, thus to a certain extent It reduces and is discharged into the pollutant component of environment, reduces production cost.
(4) research for producing propionic acid is converted about lactic acid at present only have biological fermentation process, and the present invention is spread out using biomass Biological lactic acid prepares propionic acid as raw material, proposes pioneeringly and produces propionic acid using chemical method conversion lactic acid, fast and effeciently realizes Propionic acid production based on renewable bioenergy;
(5) present invention using can by biomass energy obtain lactic acid as raw material production propionic acid, it is green non-poisonous, be not easy to produce Raw poisonous and harmful substance;
(6) propionic acid yield of the present invention is up to 58.79%, and selectivity is good, and byproduct of reaction is few.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Detailed description of the invention
Fig. 1 is the HPLC spectrogram of the product of the embodiment of the present invention 1;Wherein, RID and VWD represents the two of the liquid phase of the sample Kind signal.
Specific embodiment
The present invention provides a kind of method that lactic acid conversion produces propionic acid, the method are as follows: add lactic acid, catalyst, reducing agent Entering in water, hydro-thermal reaction is carried out under atmosphere of inert gases, reaction temperature is 175~300 DEG C, 30~180min of reaction time, Propionic acid is obtained in reaction solution.
Herein, the range indicated by " numerical value to another numerical value ", is that one kind avoids enumerating in the description The summary representation of all numerical value in the range.Therefore, the record of a certain special value range, covers the numberical range Interior any number and the relatively fractional value range defined by any number in the numberical range, as bright in the description Text writes out any number as should be compared with fractional value range.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair It is bright, rather than limit the scope of protection of the present invention.What those skilled in the art made according to the present invention in practical applications changes Into and adjustment, still fall within protection scope of the present invention.
Embodiment 1
The present embodiment is related to a kind of water of metal simple-substance (Zn powder) as reducing agent, metal simple-substance (Co powder) as catalyst The method that thermal transition lactic acid prepares propionic acid, reaction equation are as follows:
The preparation method of the present embodiment includes the following steps:
Successively lactic acid (1.5mmol, reaction density 200mmol/L), Zn powder (10mmol) and Co powder (4mmol) are packed into In the hydrothermal reactor of Teflon liner, water is added to make reactor filling rate 25%, nitrogen is filled with into reactor and excludes air Interference after seal, reactor, which is put into baking oven, makes 250 DEG C of its reaction temperature, and reaction time 120min takes out after reaction Mixture filtering can obtain propionic acid solution.
Will reaction after product propionic acid solution with HPLC analyze (see attached drawing 1), it is that Fig. 1 is shown the result shows that: propionic acid is main Product, yield is up to 58.79%.
Embodiment 2
The present embodiment is related to a kind of water of metal simple-substance (Zn powder) as reducing agent, metal simple-substance (Co powder) as catalyst The method that thermal transition lactic acid prepares propionic acid, described method includes following steps:
Successively lactic acid (1.5mmol, reaction density 200mmol/L), Zn powder (10mmol) and Co powder (4mmol) are packed into In the hydrothermal reactor of Teflon liner, water is added to make reactor filling rate 25%, nitrogen is filled with into reactor and excludes air Interference after seal, reactor, which is put into baking oven, makes 225 DEG C of its reaction temperature, and reaction time 180min takes out after reaction Mixture filtering can obtain propionic acid solution.
Product propionic acid solution after reaction is analyzed with HPLC, the results showed that propionic acid is primary product, and yield is up to 42.75%.
Embodiment 3
The present embodiment is related to a kind of water of metal simple-substance (Zn powder) as reducing agent, metal simple-substance (Co powder) as catalyst The method that thermal transition lactic acid prepares propionic acid, described method includes following steps:
Successively lactic acid (1.5mmol, reaction density 200mmol/L), Zn powder (10mmol) and Co powder (4mmol) are packed into In the hydrothermal reactor of Teflon liner, water is added to make reactor filling rate 25%, nitrogen is filled with into reactor and excludes air Interference after seal, reactor, which is put into baking oven, makes 250 DEG C, reaction time 90min of its reaction temperature, takes out after reaction mixed Propionic acid solution can be obtained by closing object filtering.
Product propionic acid solution after reaction is analyzed with HPLC, the results showed that propionic acid is primary product, and yield is up to 48.05%.
Embodiment 4
The present embodiment is related to a kind of water of metal simple-substance (Zn powder) as reducing agent, metal simple-substance (Co powder) as catalyst The method that thermal transition lactic acid prepares propionic acid, described method includes following steps:
Successively lactic acid (1.5mmol, reaction density 125mmol/L), Zn powder (10mmol) and Co powder (4mmol) are packed into In the hydrothermal reactor of Teflon liner, water is added to make reactor filling rate 40%, nitrogen is filled with into reactor and excludes air Interference after seal, reactor, which is put into baking oven, makes 250 DEG C of its reaction temperature, and reaction time 120min takes out after reaction Mixture filtering can obtain propionic acid solution.
Product propionic acid solution after reaction is analyzed with HPLC, the results showed that propionic acid is primary product, and yield is up to 54.03%.
Embodiment 5
The present embodiment is related to a kind of water of metal simple-substance (Zn powder) as reducing agent, metal simple-substance (Co powder) as catalyst The method that thermal transition lactic acid prepares propionic acid, described method includes following steps:
Successively lactic acid (1.5mmol, reaction density 250mmol/L), Zn powder (10mmol) and Co powder (4mmol) are packed into In the hydrothermal reactor of Teflon liner, water is added to make reactor filling rate 20%, nitrogen is filled with into reactor and excludes air Interference after seal, reactor, which is put into baking oven, makes 250 DEG C of its reaction temperature, and reaction time 120min takes out after reaction Mixture filtering can obtain propionic acid solution.
Product propionic acid solution after reaction is analyzed with HPLC, the results showed that propionic acid is primary product, and yield is up to 53.61%.
Embodiment 6
The present embodiment is the change case of embodiment 1, and technical solution is same as Example 1, be the difference is that only, reducing agent For metal simple-substance Al (10mmol);The filling rate of water is 25% in hydrothermal reactor;Reaction condition is 250 DEG C, 120min.
Product carries out qualitative and HPLC quantitative analysis with GC/MS after reacting, and GC/MS qualitative analysis shows based on propionic acid Product is wanted, HPLC quantitative analysis shows yield up to 52.75%.
Embodiment 7
The present embodiment is the change case of embodiment 1, and technical solution is same as Example 1, be the difference is that only, lactic acid, Catalyst (Co powder), reducing agent (metal simple-substance Zn powder) molar ratio be 1.5:2:10;The filling rate of water is in hydrothermal reactor 25%;Reaction condition is 250 DEG C, 120min.Product carries out qualitative and HPLC quantitative analysis with GC/MS after reacting, and GC/MS is fixed Property analysis shows, propionic acid is primary product, and HPLC quantitative analysis shows yield up to 36.38%.
Embodiment 8
The present embodiment is the change case of embodiment 7, and technical solution is same as Example 1, be the difference is that only, lactic acid, Catalyst (Co powder), reducing agent (metal simple-substance Zn powder) molar ratio be 1.5:10:25.
Product carries out qualitative and HPLC quantitative analysis with GC/MS after reacting, and GC/MS qualitative analysis shows based on propionic acid Product is wanted, HPLC quantitative analysis shows yield up to 56.20%.
Embodiment 9
The present embodiment is the change case of embodiment 1, and technical solution is same as Example 1, be the difference is that only, catalyst For metal oxide CuO (4mmol);The filling rate of water is 25% in hydrothermal reactor;Reaction condition is 250 DEG C, 120min.
Product carries out qualitative and HPLC quantitative analysis with GC/MS after reacting, and GC/MS qualitative analysis shows based on propionic acid Product is wanted, HPLC quantitative analysis shows that yield is 2.79%.
Embodiment 10
The present embodiment is the change case of embodiment 1, and technical solution is substantially the same manner as Example 1, the difference is that, cream Acid, catalyst (Co powder), reducing agent (metal simple-substance Zn powder) molar ratio be 1.5:2:5.
Product carries out qualitative and HPLC quantitative analysis with GC/MS after reacting, and GC/MS qualitative analysis shows based on propionic acid Product is wanted, HPLC quantitative analysis shows that yield is 6.21%.
Embodiment 11
The present embodiment is the change case of embodiment 1, and technical solution is substantially the same manner as Example 1, the difference is that, hydro-thermal Reactor is set to 175 DEG C of reaction 60min.
Product carries out qualitative and HPLC quantitative analysis with GC/MS after reacting, and GC/MS qualitative analysis shows based on propionic acid Want product, HPLC quantitative analysis shows yield highest only 1.65%.
Embodiment 12
The present embodiment is the change case of embodiment 1, and technical solution is same as Example 1, the difference is that, reducing agent is Metal simple-substance Fe (10mmol).
Product carries out qualitative and HPLC quantitative analysis with GC/MS after reacting, and GC/MS qualitative analysis shows based on propionic acid Product is wanted, HPLC quantitative analysis shows that yield is 1.15%.
Embodiment 13
The present embodiment uses the lactic acid of biomass source, and general scheme is as follows:
Wherein, first step reaction condition are as follows: 0.01M NaOH, 0.01M Ni2+, 0.035g biomass, 2mL H2O,300 DEG C, 1min, the biomass is glucose, cellulose or starch.Then contain lactic acid using what the first step obtained after reaction Solution carry out the reaction that the conversion of second step lactic acid produces propionic acid, reaction condition are as follows: 0.76mmol Co, 1.9mmol Zn, 300 DEG C, 60min.The yield results of final reacting product are as shown in table 1 below.
Table 1
The present embodiment is able to demonstrate that the lactic acid of biomass source effectively can be converted to propionic acid by method of the invention.
Wherein, remaining metal simple-substance and remaining metallic compound can be recovered or make after reaction under hydrothermal condition Other production purposes, to reduce the pollutant component for being discharged into environment to a certain extent.
Under the teaching of the present invention and the above embodiments, those skilled in the art are easy to it is envisioned that cited by the present invention Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring substantive content of the invention.

Claims (8)

1.一种乳酸转化产丙酸的方法,其特征在于,所述方法为:将乳酸、催化剂、还原剂加入水中,在惰性气体氛围下进行水热反应,反应温度为175~300℃,反应时间30~180min,在反应液中即得到丙酸;其中,所述乳酸、催化剂、还原剂的反应摩尔比为1.5:(2~10):(5~25);其中,所述催化剂选自Co、Ni、Cu、Fe、Fe2O3、CuO、Cu2O、Ni2O3或Fe3O4的一种;所述还原剂为金属单质粉末,所述金属单质为Al、Fe、Mn或Zn。1. a method for lactic acid conversion to produce propionic acid, is characterized in that, described method is: lactic acid, catalyzer, reducing agent are added in water, carry out hydrothermal reaction under inert gas atmosphere, temperature of reaction is 175~300 ℃, reaction Time 30-180min, propionic acid is obtained in the reaction solution; wherein, the reaction molar ratio of the lactic acid, the catalyst and the reducing agent is 1.5:(2-10):(5-25); wherein, the catalyst is selected from One of Co, Ni, Cu, Fe, Fe 2 O 3 , CuO, Cu 2 O, Ni 2 O 3 or Fe 3 O 4 ; the reducing agent is a metal element powder, and the metal element is Al, Fe, Mn or Zn. 2.如权利要求1所述的乳酸转化产丙酸的方法,其特征在于,将反应结束后得到的反应体系进行过滤,即得到丙酸溶液。2. the method for lactic acid conversion to produce propionic acid as claimed in claim 1 is characterized in that, the reaction system obtained after the reaction finishes is filtered, namely obtains propionic acid solution. 3.如权利要求1所述的乳酸转化产丙酸的方法,其特征在于,所述乳酸、催化剂、还原剂的摩尔比为1.5:(4~6):(10~15)。3 . The method for converting lactic acid to produce propionic acid according to claim 1 , wherein the molar ratio of the lactic acid, the catalyst and the reducing agent is 1.5:(4-6):(10-15). 4 . 4.如权利要求1所述的乳酸转化产丙酸的方法,其特征在于,所述乳酸的反应浓度为100~250mmol/L。4. The method for converting lactic acid to produce propionic acid according to claim 1, wherein the reaction concentration of the lactic acid is 100-250 mmol/L. 5.如权利要求1所述的乳酸转化产丙酸的方法,其特征在于,所述还原剂为金属单质Zn粉末,所述催化剂为Co。5 . The method for converting lactic acid to produce propionic acid according to claim 1 , wherein the reducing agent is metal elemental Zn powder, and the catalyst is Co. 6 . 6.如权利要求1所述的乳酸转化产丙酸的方法,其特征在于,所述方法包括如下步骤:6. the method for lactic acid conversion to produce propionic acid as claimed in claim 1, is characterized in that, described method comprises the steps: A、向水热反应器中依次加入乳酸、催化剂、还原剂及水;A, add lactic acid, catalyzer, reducing agent and water successively to hydrothermal reactor; B、向上述水热反应器中充入氮气并密封;B, in the above-mentioned hydrothermal reactor, nitrogen is charged and sealed; C、将上述水热反应器置于175~300℃条件下反应30~180min;C, above-mentioned hydrothermal reactor is placed under 175~300 ℃ of conditions to react 30~180min; D、反应结束后,过滤,即得丙酸溶液。D. After the reaction is finished, filter to obtain propionic acid solution. 7.如权利要求1所述的乳酸转化产丙酸的方法,其特征在于,所述乳酸为生物质衍生物乳酸。7. The method for converting lactic acid to produce propionic acid according to claim 1, wherein the lactic acid is a biomass derivative lactic acid. 8.如权利要求1或5所述的乳酸转化产丙酸的方法,其特征在于,所述反应温度为225~250℃。8. The method for converting lactic acid to produce propionic acid according to claim 1 or 5, wherein the reaction temperature is 225-250°C.
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