CN104402677B - Utilize the method that biomass derivatives lactic acid prepares 1,2-propane diols - Google Patents
Utilize the method that biomass derivatives lactic acid prepares 1,2-propane diols Download PDFInfo
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- CN104402677B CN104402677B CN201410640709.8A CN201410640709A CN104402677B CN 104402677 B CN104402677 B CN 104402677B CN 201410640709 A CN201410640709 A CN 201410640709A CN 104402677 B CN104402677 B CN 104402677B
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- lactic acid
- hydrothermal reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a kind of method utilizing biomass derivatives lactic acid to prepare 1,2 propane diols；Described method comprises the steps: to be sequentially added into catalyst, reducing agent, lactic acid solution in hydrothermal reactor；In above-mentioned hydrothermal reactor, it is filled with nitrogen and seals；30～210min are reacted under the conditions of above-mentioned hydrothermal reactor is placed in 150～300 DEG C；After reaction terminates, filter, obtain 1,2 propane diols.This method can efficiently, highly selective synthesize 1,2 propane diols.This method uses the reproducible biomass derivatives being widely present in nature as raw materials for production, avoid traditional industry preparation method needing consume a large amount of fossil fuel, without the complicated effective catalyst of preparation, simple to operate, conversion ratio is high, without pure hydrogen, use water as hydrogen source and reaction dissolvent environmental pollution is little, beneficially industrialized production.
Description
Technical field
The invention belongs to derived energy chemical technical field, be specifically related to one and utilize biomass derivatives lactic acid to prepare 1,2-the third two
The method of alcohol.
Background technology
In having entered since 21 century, along with the step of whole world modernization, fossil fuel potential energy starved crisis,
Particularly from Petroleum refining gasoline out, it it is the reason causing Global Oil crisis.Therefore, reduce fossil combustion
The dependence of material, develops new reproducible clean energy resource and is more and more paid close attention to by people.The most industrial
Wide variety of 1,2-PD synthetic method is mainly prepared through catalytic hydration by expoxy propane, and this technique mainly has
The shortcomings such as follow-up equipment (evaporation, rectifying) long flow path or severe reaction conditions, energy consumption is high, 1,2-PD yield is low,
And non-renewable due to petroleum resources, reserves are inevitable the most exhausted, produce 1,2-hence with reproducible raw material
Propane diols is imperative.Biomass energy has what recyclability, low stain, widely distributed property and total amount were enriched due to it
Feature, has the biggest application prospect.
Summary of the invention
For defect of the prior art, it is an object of the invention to provide a kind of novel high-efficient simple utilizes living beings
The method that derivative lactic acid (DL type) prepares 1,2-propane diols.The method transformation efficiency is high, good product selectivity,
Without the noble metal catalyst using complicated difficult to prepare, simple to operate；Making solvent with water and replace hydrogen source, environmental pollution is little,
Energy consumption is low, beneficially industrialized production.Product 1,2-PD, as a kind of important intermediate chemical and solvent, is ring
Epoxy resins, polyurethane resin, unsaturated polyester (UP), plasticizer, curing agent, the important source material of surfactant, also by extensively
General as hygroscopic agent, antifreeze, lubricant, emulsifying agent and pharmacy.
It is an object of the invention to be achieved through the following technical solutions:
The present invention relates to a kind of method utilizing biomass derivatives lactic acid to prepare 1,2-PD, described method includes as follows
Step:
A, in hydrothermal reactor, it is sequentially added into lactic acid, catalyst, reducing agent and water；
B, in above-mentioned hydrothermal reactor, it is filled with nitrogen and seals；
C, above-mentioned hydrothermal reactor is placed in 150～300 DEG C under the conditions of react 30～210min；
After D, reaction terminate, filter, obtain 1,2-PD.
Preferably, in step A, described lactic acid, catalyst, the mol ratio of reducing agent are 1:(3～18): (12～48).
It is highly preferred that the mol ratio of described lactic acid, catalyst, reducing agent is 1:(3～8): (30～42).
It is highly preferred that the mol ratio of described lactic acid, catalyst, reducing agent is 1:6:36.
Preferably, in step A, the concentration of described lactic acid is for for 6.25～25g/L.
Preferably, in step A, in described hydrothermal reactor, the filling rate of water is 10～40%.
Preferably, in step A, described catalyst includes metal or metal oxide.
Preferably, described catalyst is Cu, Fe, Co, Ni, Fe2O3、Ni2O3、Fe3O4, CuO or Cu2O。
It is highly preferred that described catalyst is CuO.
Preferably, in step A, described reducing agent includes metal simple-substance powder.
Preferably, described metal simple-substance is Al, Fe, Mg or Zn.
It is highly preferred that described metal simple-substance is Zn.
In step B, described nitrogen be added to fully discharge air, in order to avoid the possible composition in air to reaction
Impact.
Preferably, in step C, described hydrothermal reactor is placed in baking oven.
In step C, water in hydrothermal reactor under the conditions of 150～300 DEG C react 30～210min HTHP
Water；The dielectric constant of high-temperature high pressure water reduces, and intermolecular hydrogen bond weakens, and isothermal compressibility improves, ion constant (Kw)
1000 times are almost added than normal-temperature water.
Preferably, in step C, described course of reaction is: reducing agent and water react generation in-situ hydrogen, and then in-situ hydrogen
Under catalyst action, there are two step reduction reactions, so the present invention is in the condition without being additionally passed through pure hydrogen with lactic acid
Complete the synthesis of 1,2-propane diols；Additionally, said process there is also some possible side reaction processes.The most such as
Under:
Preferably, in step D, described filtration is specially and uses the filter membrane of 0.45 μm to filter.
Compared with prior art, the present invention has a following beneficial effect:
(1) present invention uses biomass derivatives lactic acid to make raw material 1,2-PD, and lactic acid can be from biomass resource
Glucose (nature green plants can be obtained in a large number by photosynthesis) prepares, it is not necessary to consume fossil energy, can part
Alleviate the energy problem that nowadays whole world faces；
(2) course of reaction of the present invention generates high-temperature high pressure water and make reaction dissolvent, compared with light water, high-temperature high pressure water
Dielectric constant reduce, intermolecular hydrogen bond weakens, isothermal compressibility improve, ion constant (Kw) more several than normal-temperature water
Add 1000 times, utilize these characteristics of high-temperature high pressure water, can realize with metal cheap and easy to get and compound thereof
Make reducing agent and lactic acid transformed into 1,2-PD this high added value organic matter by catalyst under hydrothermal conditions, it is achieved
Efficient low-consume converts organic resource；
(3) present invention is without being additionally passed through high-purity hydrogen, significantly reduces energy consumption of reaction, and more environmental protection,
Environmental pollution is little；
(4) present invention uses metal cheap and easy to get and metal oxide to make catalyst, it is not necessary to the noble metal that preparation is complicated
Catalyst, reduces reaction cost；
(5) without adding acid, alkali, reaction condition is gentle, production safety；
(6) 1,2-PD productivity of the present invention is up to 93%, and the best, byproduct of reaction is few；
(7) in the inventive method, reducing agent and catalyst can be recovered or make other and produce purposes, thus to a certain extent
Reduce and enter the pollutant component of environment, reduce production cost.
Accompanying drawing explanation
The detailed description made non-limiting example with reference to the following drawings by reading, other of the present invention is special
Levy, purpose and advantage will become more apparent upon:
Fig. 1 is the GC/MS spectrogram of the product of embodiment 1；
Fig. 2 is the HPLC spectrogram of the product of embodiment 1.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in those skilled in the art
Member is further appreciated by the present invention, but limits the present invention the most in any form.It should be pointed out that, the common skill to this area
For art personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into
Protection scope of the present invention.
Embodiment 1
The present embodiment relates to a kind of metal simple-substance (Zn powder), metal oxide (CuO powder) hydrothermal conversion lactic acid prepares 1,2-
The method of propane diols, reaction equation is as follows:
Described method comprises the steps:
Successively by lactic acid (75mg, reaction density is 7.14g/L), Zn powder (30mmol) and CuO powder (5mmol)
Loading in the hydrothermal reactor of Teflon liner, adding water and making reactor filling rate is 35%, is filled with nitrogen row in reactor
Except sealing after the interference of air, being put into by reactor in baking oven and making its reaction temperature is 250 DEG C, reaction time 120min,
Take out mixture after reaction and filter to obtain 1,2-propane diols.
Reaction afterproduct GC/MS carries out qualitative (see Fig. 1) and HPLC quantitative analysis (see Fig. 2), and GC/MS is qualitative
Analysis shows, 1,2-PD is primary product, and HPLC quantitative analysis shows, productivity reaches as high as 93%.
Embodiment 2
The present embodiment relates to a kind of metal simple-substance (Zn powder), metal oxide (CuO powder) hydrothermal conversion lactic acid prepares 1,2-
The method of propane diols, described method comprises the steps:
Successively by lactic acid (75mg, reaction density is 10g/L), Zn powder (30mmol) and CuO powder (5mmol)
Loading in the hydrothermal reactor of Teflon liner, adding water and making reactor filling rate is 25%, is filled with nitrogen row in reactor
Except sealing after the interference of air, being put into by reactor in baking oven and making its reaction temperature is 250 DEG C, reaction time 120min,
Take out mixture after reaction and filter to obtain 1,2-propane diols.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity reaches as high as 86%.
Embodiment 3
The present embodiment relates to a kind of metal simple-substance (Zn powder), metal oxide (CuO powder) hydrothermal conversion lactic acid prepares 1,2-
The method of propane diols, described method comprises the steps:
Successively lactic acid (75mg, reaction density is 25g/L), Zn powder (30mmol) and CuO powder (3mmol) are filled
Entering in the hydrothermal reactor of Teflon liner, adding water and making reactor filling rate is 10%, is filled with nitrogen and gets rid of in reactor
Sealing after the interference of air, being put into by reactor in baking oven and making its reaction temperature is 250 DEG C, reaction time 120min, instead
Take out mixture after should and filter to obtain 1,2-propane diols.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity reaches as high as 90%.
Embodiment 4
The present embodiment relates to a kind of metal simple-substance (Zn powder), metal oxide (CuO powder) hydrothermal conversion lactic acid prepares 1,2-
The method of propane diols, described method comprises the steps:
Successively lactic acid (75mg), Zn powder (40mmol) and CuO powder (5mmol) are loaded the water of Teflon liner
In thermal reactor, adding water and making reactor filling rate is 25%, seals after being filled with the interference of nitrogen eliminating air in reactor,
Being put into by reactor in baking oven and making its reaction temperature is 250 DEG C, reaction time 120min, takes out mixture and filter after reaction
1,2-propane diols.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity reaches as high as 90%.
Embodiment 5
The present embodiment is the change case of embodiment 1, and technical scheme is same as in Example 1, the difference is that only, catalysis
Agent is metal simple-substance Cu (5mmol)；In hydrothermal reactor, the filling rate of water is 25%；Reaction condition is 250 DEG C, 150min.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity reaches as high as 61%.
Embodiment 6
The present embodiment is the change case of embodiment 1, and technical scheme is same as in Example 1, the difference is that only, lactic acid,
Catalyst (CuO powder), the mol ratio of reducing agent (metal simple-substance Zn powder) are 1:3:30；In hydrothermal reactor, water fills out
The rate of filling is 40%；Reaction condition is 300 DEG C, 30min.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity reaches as high as 74%.
Embodiment 7
The present embodiment is the change case of embodiment 1, and technical scheme is same as in Example 1, the difference is that only, lactic acid,
Catalyst (CuO powder), the mol ratio of reducing agent (metal simple-substance Zn powder) are 1:8:42.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity reaches as high as 90%.
Comparative example 1
This comparative example is the comparative example of embodiment 1, and technical scheme is substantially the same manner as Example 1, and difference is, breast
Acid, catalyst (CuO powder), the mol ratio of reducing agent (metal simple-substance Zn powder) are 1:2:12.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity is only 7%.
Comparative example 2
This comparative example is the comparative example of embodiment 1, and technical scheme is substantially the same manner as Example 1, and difference is, water
Thermal reactor is arranged at 140 DEG C of reaction 60min.
Reaction afterproduct GC/MS carries out qualitative and HPLC quantitative analysis, and GC/MS qualitative analysis shows, 1,2-the third two
Alcohol is primary product, and HPLC quantitative analysis shows, productivity is the highest by only 5%.
Comparative example 3
This comparative example is the comparative example of embodiment 1, also belongs to existing conventional techniques；This comparative example technical scheme and embodiment 1
Identical, difference is, hydrogen source comes as additional high-purity hydrogen, and is not added with reducing agent；By reaction afterproduct GC/MS
Carrying out qualitative and HPLC quantitative analysis, GC/MS qualitative analysis shows, containing 1,2-PD in product, but HPLC is fixed
Component analysis shows, productivity is only 42%.
Above mentioned embodiment provide the method utilizing biomass derivatives lactic acid to prepare 1,2-PD, on-demand in commercial Application
Seeking the suitable hydrothermal reactor of employing, can control reaction temperature is 150～300 DEG C, and water filling rate is 10～40%, instead
Answer 30～210min.
Wherein, after under hydrothermal condition, reaction terminates, the metal simple-substance of residual and the metallic compound of residual can be recovered or make it
He produces purposes, thus reduces the pollutant component entering environment to a certain extent.
In sum, compared with prior art, advantageous effect is notable, illustrates that the present invention has prominent substance for the present invention
Feature and marked improvement, because creative.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in
Stating particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims,
This has no effect on the flesh and blood of the present invention.
Claims (2)
1. one kind utilizes the method that biomass derivatives lactic acid prepares 1,2-PD, it is characterised in that described method bag
Include following steps:
A, in hydrothermal reactor, it is sequentially added into lactic acid, catalyst, reducing agent and water；
B, be filled with in above-mentioned hydrothermal reactor nitrogen punching catch up with air and seal；
C, above-mentioned hydrothermal reactor is placed in 150～300 DEG C under the conditions of react 30～210min；
After D, reaction terminate, filter, obtain 1,2-PD；
Described catalyst is CuO；
Described lactic acid, catalyst, the mol ratio of reducing agent are 1:(3～8): (30～42), in described hydrothermal reactor
Water filling rate is 10～40%；
The concentration of described lactic acid aqueous solution is 6.25～25g/L；
Described reducing agent is metal simple-substance powder；Wherein, described metal simple-substance is Al, Fe, Mg or Zn.
The method utilizing biomass derivatives lactic acid to prepare 1,2-PD the most according to claim 1, its feature
Being, in step D, described filtration is specially and uses the filter membrane of 0.45 μm to filter.
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| CN106117035B (en) * | 2016-06-30 | 2019-02-22 | 上海交通大学 | A kind of method that lactic acid conversion produces propionic acid |
| CN106349014B (en) * | 2016-08-23 | 2020-08-18 | 上海交通大学 | Method for preparing 1, 4-pentanediol by utilizing levulinic acid ester |
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