CN107597116A - A kind of method that 1,4 pentanediols are prepared by copper-based catalysts direct hydrogenation levulic acid - Google Patents
A kind of method that 1,4 pentanediols are prepared by copper-based catalysts direct hydrogenation levulic acid Download PDFInfo
- Publication number
- CN107597116A CN107597116A CN201710621151.2A CN201710621151A CN107597116A CN 107597116 A CN107597116 A CN 107597116A CN 201710621151 A CN201710621151 A CN 201710621151A CN 107597116 A CN107597116 A CN 107597116A
- Authority
- CN
- China
- Prior art keywords
- copper
- nitrae
- pentanediol
- isosorbide
- levulic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It is a kind of that the method for Isosorbide-5-Nitrae pentanediol is prepared by copper-based catalysts direct hydrogenation levulic acid, it is characterized in that comprising the following steps：Under the conditions of existing for copper-based catalysts in Isosorbide-5-Nitrae pentanediol, reaction dissolvent and reactant levulic acid are directly mixed, hydrogen is passed through and carries out a cooking-pot type hydrogenation reaction, obtain Isosorbide-5-Nitrae pentanediol after completion of the reaction；Compared with prior art, the present invention has prepared cheap base metal new type copper base catalyst, and its synthetic method is simple, and cost is cheap, nontoxic, is easy to large-scale production, while has magnetic, reclaims and reuses after easy to use；It can efficiently be realized with the catalyst and Isosorbide-5-Nitrae pentanediol is converted into by levulic acid direct hydrogenation, selectivity is good, and the gross production rate of Isosorbide-5-Nitrae pentanediol may be up to 85%, show that the synthetic process has higher potential age deduction.
Description
Technical field
The invention belongs to chemical technology field, is related to a kind of novel copper-based hydrogenation reaction towards Isosorbide-5-Nitrae-pentanediol synthesis and urges
The composition and preparation method of agent, and the preparation method for using the catalyst directly to synthesize Isosorbide-5-Nitrae-pentanediol by levulic acid.
Background technology
As the important substance basis of human survival and development, fossil resource supports 19th century to 20th century nearly 200 years
Carry out progress and the socio-economic development of human civilization.They are not only the main energy of mankind's consumption, and meet mankind's day
The raw material of Chang Suoxu various chemicals.However, huge consumption of the non-renewable and mankind of fossil resource to it, makes fossil
The energy is gradually moving towards exhausted.In order to solve energy crisis, numerous Scientific Research Workers are directed to developing solar energy, wind
The new energy such as energy, nuclear energy, but can not solve resource sex chromosome mosaicism.And by developing biomass, it can both use biomass energy solution
Certainly energy crisis, the fossil resources such as oil, the basic material as various chemicals can also be replaced with biomass resource.
Isosorbide-5-Nitrae-pentanediol is a kind of potential polyester-based polymer monomer, and polyester material can be made with diacid reactant, because
And demand is huge.At present, the production of Isosorbide-5-Nitrae-pentanediol is also relatively difficult, and feasible production line is mainly by levulic acid, second
Acyl propionic ester and gamma-valerolactone catalytic hydrogenation.Levulinate is with gamma-valerolactone mainly by biomass hydrolysate second
Acyl propionic acid produces, and the production process of separation adds the manufacturing cost of Isosorbide-5-Nitrae-pentanediol.Directly added by levulic acid catalysis
Hydrogen produces Isosorbide-5-Nitrae-pentanediol, and reaction condition is extremely harsh, can only use noble metal catalyst at present, the limitation of reaction condition with it is expensive
The expensive cost of metallic catalyst, constrains the large-scale production of Isosorbide-5-Nitrae-pentanediol.However, up to now, it is efficiently recyclable and
Cheap non-precious metal catalyst is used to inside and outside the producing country of 1,4- pentanediols have not been reported.Therefore new and economic height is developed
The catalyst of effect is particularly significant for directly producing Isosorbide-5-Nitrae-pentanediol by levulic acid.
The content of the invention
It is an object of the invention to provide a kind of side that 1,4- pentanediols are prepared by copper-based catalysts direct hydrogenation levulic acid
Method, including a kind of Hydrogenation is for the method for the copper-based catalysts of Isosorbide-5-Nitrae-pentanediol, and on this catalyst it is achievable by second
Acyl propionic acid direct hydrogenation efficiently prepares the new method of 1,4- pentanediols.
A kind of method of copper-based catalysts of the Hydrogenation of the present invention for Isosorbide-5-Nitrae-pentanediol, it is characterised in that its main body
Active component is copper, and using iron and boron as co-catalysis component, the percentage by weight of three kinds of elements is in catalyst：Copper content is 50%-
99%, iron content 0.9%-40%, Boron contents 0.1%-10%.Such copper-based catalysts, using solution phase chemical reduction system
Standby, specific preparation process is as follows：The salting liquid A that total metal concentration comprising copper and iron is 0.01-2mol/L is prepared, is passed through nitrogen
Protection, is placed in ice-water bath, machinery is stirred vigorously；The reducing agent mixed liquid B prepared is added dropwise to salting liquid with peristaltic pump
In, time for adding 1-2h；Continue to react 2h after being added dropwise to wait abundant reduction；Reacted product is filtered,
Filtered 5 times with deionized water, absolute ethyl alcohol filters 3 times；Obtained catalyst is stored in absolute ethyl alcohol.
Described salting liquid A, its total metal salt solution concentration is preferably 0.1mol/L；Its iron accounts for total metal molar ratio control
System is within 50%.
Described salting liquid solvent is water, ethanol, methanol or ethylene glycol, preferably water；Metal salt is nitrate or chlorination
Salt, preferably nitrate.
Described reducing agent mixed liquid B, its reducing agent are sodium borohydride or potassium borohydride, preferably sodium borohydride；It is mixed
It is 2mol/L to close reductant concentration in liquid B, and solvent is water；Reducing agent total amount and the mol ratio control of metal in salting liquid A are 4 ﹕
1；It is 12-14 that sodium hydroxide solution regulation pH value is added in mixed liquid B, and concentration of sodium hydroxide solution used is 0.2mol/L.
A kind of method that Isosorbide-5-Nitrae-pentanediol is prepared by copper-based catalysts direct hydrogenation levulic acid of the present invention, including
Following steps：It is under the conditions of existing for the made copper-based catalysts of above-mentioned condition, reaction dissolvent and reactant levulic acid is direct
Mixing, it is passed through hydrogen and carries out a cooking-pot type hydrogenation reaction, obtain Isosorbide-5-Nitrae-pentanediol after completion of the reaction.
Described reaction dissolvent includes one or two kinds of in water, methanol, ethanol, dodecane, ether or 1,4- dioxane
More than, preferred Isosorbide-5-Nitrae-dioxane.Preparation condition：The concentration control of levulic acid is 0.1-0.5 mol/L, and reaction temperature is
60-250 DEG C, Hydrogen Vapor Pressure 0.1-6Mpa, the reaction time is 0.1-24h.
The technique effect of the present invention：Compared with prior art, cheap base metal new type copper base catalyst has been prepared,
Its synthetic method is simple, and cost is cheap, nontoxic, is easy to large-scale production, while has magnetic, it is easy to use after recovery and
Reuse；It can efficiently be realized with the catalyst and Isosorbide-5-Nitrae pentanediol is converted into by levulic acid direct hydrogenation, selectivity is good, Isosorbide-5-Nitrae-
The gross production rate of pentanediol may be up to 85 %, show that the synthetic process has higher potential age deduction.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of catalyst of the present invention.
Fig. 2 is nitrogen desorption absorption (BET) collection of illustrative plates of catalyst of the present invention.
Fig. 3 is transmission electron microscope (TEM) figure of catalyst of the present invention, and figure (a) is overall pattern, figure（b）For particle
Pattern.
Embodiment
According to following embodiments, the present invention may be better understood.Content described by embodiment is merely to illustrate this hair
It is bright, without should be also without limitation on the present invention described in detail in claims.
Embodiment 1.
Catalyst 30%FeCuB preparation：30%, which represents iron, accounts for total metal（Iron+copper）Molar ratio is 30%, prepares and includes nine
Water ferric nitrate 1.01g, nitrate trihydrate copper 5.45g and water 250ml salting liquid A.Nitrogen protection is passed through, is placed in ice-water bath,
Machinery is stirred vigorously.Prepare the reducing agent mixed liquid B for including sodium borohydride 3.79g, sodium hydroxide 0.4g and water 50ml.It will prepare
Good reducing agent mixed liquid B is added dropwise in salting liquid A with peristaltic pump, and time for adding is to continue to react 2h after 1.5h. is added dropwise
To wait fully reduction.Reacted product is filtered, filtered 5 times with deionized water, absolute ethyl alcohol filters 3 times.Will
To catalyst 30%FeCuB be stored in absolute ethyl alcohol.
Analysis：By X-ray diffraction（XRD）, transmission electron microscope（TEM）, with N2Physical absorption（BET）To 30%FeCuB
Sample is characterized.Shown by Fig. 1,30%FeCuB samples can observe the diffraction maximum of clearly metallic copper and cuprous oxide, say
The active ingredient copper of bright catalyst is in a kind of crystalline structure.And the diffraction maximum of iron species is not found, may be due to iron species
The smaller identification range beyond XRD of crystal grain, or in a kind of amorphous structure.Characterized by BET, as shown in Figure 2,
The specific surface area of 30%FeCuB samples is 100.3m2/g.By projection electron microscope, Fig. 3（a）It is in fine particle that catalyst, which can be observed,
Shape is distributed, and is uniformly wrapped among another light material.Fig. 3（b）It was observed that single catalyst granules is about in 10nm-
Between 40nm.
Levulic acid hydrogenation activity is tested：By 0.3g levulic acids, 0.1g30%FeCuB catalyst, 15ml1,4- dioxies six
Ring, it is fitted into autoclave polytetrafluoroethyllining lining.Replaced 5 times with hydrogen after autoclave sealing, to remove the air in kettle.
Constant Hydrogen Vapor Pressure starts to react after reaction temperature is heated to after preliminary filling hydrogen, and reaction temperature is 200 DEG C, Hydrogen Vapor Pressure 5Mpa,
800 revs/min of mixing speed, reaction time 6h.After reaction terminates, room temperature is cooled to, opens reactor, product is examined with GC/MS
Survey.Levulic acid conversion ratio 100%, Isosorbide-5-Nitrae pentanediol yield 85.1%.Remaining product is gamma-valerolactone.
Embodiment 2.
Catalyst 20%FeCuB preparation：Preparation includes nine water ferric nitrate 4.04g, nitrate trihydrate copper 9.67g and water 500ml
Salting liquid A.Nitrogen protection is passed through, is placed in ice-water bath, machinery is stirred vigorously.Preparation includes sodium borohydride 7.57g, hydrogen-oxygen
Change sodium 0.8g and water 100ml reducing agent mixed liquid B.The reducing agent mixed liquid B prepared is added dropwise to salting liquid A with peristaltic pump
In, time for adding is to continue to react 2h to wait abundant reduction after 1.5h. is added dropwise.Reacted product is filtered,
Filtered 5 times with deionized water, absolute ethyl alcohol filters 3 times.Obtained catalyst 20%FeCuB is stored in absolute ethyl alcohol.
Levulic acid hydrogenation activity is tested：By 0.3g levulic acids, 0.1g20%FeCuB catalyst, 15ml ethanol, load
In autoclave polytetrafluoroethyllining lining.Replaced 5 times with hydrogen after autoclave sealing, to remove the air in kettle.It is flushed with hydrogen in advance
Constant Hydrogen Vapor Pressure starts to react after reaction temperature is heated to after gas, and reaction temperature is 200 DEG C, Hydrogen Vapor Pressure 5Mpa, stirring speed
800 revs/min of degree, reaction time 6h.After reaction terminates, room temperature is cooled to, opens reactor, product is detected with GC/MS.Acetyl
Propionic acid rate 100%, Isosorbide-5-Nitrae pentanediol yield 42.1%.Remaining product is gamma-valerolactone and ethyl levulinate.
Embodiment 3.
Catalyst 40%FeCuB preparation：Preparation includes nine water ferric nitrate 4.03g, nitrate trihydrate copper 3.62g and water 250ml
Salting liquid A.Nitrogen protection is passed through, is placed in ice-water bath, machinery is stirred vigorously.Preparation includes sodium borohydride 3.78g, hydrogen-oxygen
Change sodium 0.4g and water 50ml reducing agent mixed liquid B.The reducing agent mixed liquid B prepared is added dropwise to salting liquid A with peristaltic pump
In, time for adding is to continue to react 2h to wait abundant reduction after 1.5h. is added dropwise.Reacted product is filtered,
Filtered 5 times with deionized water, absolute ethyl alcohol filters 3 times.Obtained catalyst 40%FeCuB is stored in absolute ethyl alcohol.
Levulic acid hydrogenation activity is tested：By 0.3g levulic acids, 0.1g40%FeCuB catalyst, 15ml1,4- dioxies six
Ring, it is fitted into autoclave polytetrafluoroethyllining lining.Replaced 5 times with hydrogen after autoclave sealing, to remove the air in kettle.
Constant Hydrogen Vapor Pressure starts to react after reaction temperature is heated to after preliminary filling hydrogen, and reaction temperature is 200 DEG C, Hydrogen Vapor Pressure 5Mpa,
800 revs/min of mixing speed, reaction time 6h.After reaction terminates, room temperature is cooled to, opens reactor, product is examined with GC/MS
Survey.Levulic acid conversion ratio 100%, Isosorbide-5-Nitrae pentanediol yield 73.8%.Remaining product is gamma-valerolactone.
Embodiment 4.
Catalyst 20%FeCuB preparation：Preparation includes nine water ferric nitrate 2.02g, nitrate trihydrate copper 4.835g and water
250ml salting liquid A.Nitrogen protection is passed through, is placed in ice-water bath, machinery is stirred vigorously.Preparation includes sodium borohydride
3.79g, sodium hydroxide 0.4g and water 50ml reducing agent mixed liquid B.The reducing agent mixed liquid B prepared is added dropwise with peristaltic pump
Into salting liquid A, time for adding is to continue to react 2h to wait abundant reduction after 1.5h. is added dropwise.By reacted product
Filtered, filtered 5 times with deionized water, absolute ethyl alcohol filters 3 times.Obtained catalyst 20%FeCuB is stored in anhydrous second
In alcohol.
Levulic acid hydrogenation activity is tested：By 0.3g levulic acids, 0.1g20%FeCuB catalyst, 15ml1,4- dioxies six
Ring, it is fitted into autoclave polytetrafluoroethyllining lining.Replaced 5 times with hydrogen after autoclave sealing, to remove the air in kettle.
Constant Hydrogen Vapor Pressure starts to react after reaction temperature is heated to after preliminary filling hydrogen, and reaction temperature is 120 DEG C, Hydrogen Vapor Pressure 3Mpa,
800 revs/min of mixing speed, reaction time 6h.After reaction terminates, room temperature is cooled to, opens reactor, product is examined with GC/MS
Survey.Levulic acid conversion ratio 100%, Isosorbide-5-Nitrae pentanediol yield 0.5%.Remaining product is gamma-valerolactone（Yield>99%）.
The present invention can also have other various embodiments, in the case of without departing substantially from spirit of the invention and its essence, be familiar with this
The technical staff in field can make corresponding change and deformation according to the present invention, but these corresponding changes and deformation should all belong to
Protection scope of the present invention.
Claims (3)
- A kind of 1. method that Isosorbide-5-Nitrae-pentanediol is prepared by copper-based catalysts direct hydrogenation levulic acid, it is characterized in that including following step Suddenly：Under the conditions of existing for copper-based catalysts in Isosorbide-5-Nitrae-pentanediol, reaction dissolvent and reactant levulic acid are directly mixed, led to Enter hydrogen and carry out a cooking-pot type hydrogenation reaction, obtain Isosorbide-5-Nitrae-pentanediol after completion of the reaction；Described reaction dissolvent includes one or more kinds of in water, methanol, ethanol, dodecane, ether or 1,4- dioxane； The concentration control of levulic acid is 0.1-0.5 mol/L, and reaction temperature is 60-250 DEG C, Hydrogen Vapor Pressure 0.1-6Mpa, reaction Time is 0.1-24h；The method of the copper-based catalysts of described Isosorbide-5-Nitrae-pentanediol, its main body active component are copper, using iron and boron as co-catalysis group Point, the percentage by weight of three kinds of elements is in catalyst：Copper content is 50%-99%, iron content 0.9%-40%, and Boron contents are 0.1%-10%；Step is as follows：The salting liquid A that total metal concentration comprising copper and iron is 0.01-2mol/L is prepared, is passed through nitrogen guarantor Shield, is placed in ice-water bath, machinery is stirred vigorously；The reducing agent mixed liquid B prepared is added dropwise in salting liquid with peristaltic pump, Time for adding is 1-2h；Continue to react 2h after being added dropwise to wait abundant reduction；Reacted product is filtered, spent Ionized water filters 5 times, and absolute ethyl alcohol filters 3 times；Obtained catalyst is stored in absolute ethyl alcohol；Described reducing agent mixed liquid B, its reducing agent are sodium borohydride or potassium borohydride；Reductant concentration is in mixed liquid B 2mol/L, solvent are water；Reducing agent total amount and the mol ratio control of metal in salting liquid A are 4;1；Hydrogen is added in mixed liquid B Sodium hydroxide solution regulation pH value is 12-14, and concentration of sodium hydroxide solution used is 0.2mol/L.
- A kind of 2. side that 1,4- pentanediols are prepared by copper-based catalysts direct hydrogenation levulic acid according to claim 1 Method, it is characterized in that described salting liquid A, its total metal salt solution concentration is 0.1mol/L；Its iron accounts for total metal molar ratio control System is within 50%.
- A kind of 3. side that 1,4- pentanediols are prepared by copper-based catalysts direct hydrogenation levulic acid according to claim 1 Method, it is characterized in that described salting liquid solvent is water, ethanol, methanol or ethylene glycol；Metal salt is nitrate or chlorate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710621151.2A CN107597116B (en) | 2017-07-27 | 2017-07-27 | Method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using copper-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710621151.2A CN107597116B (en) | 2017-07-27 | 2017-07-27 | Method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using copper-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107597116A true CN107597116A (en) | 2018-01-19 |
| CN107597116B CN107597116B (en) | 2020-03-13 |
Family
ID=61060004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710621151.2A Active CN107597116B (en) | 2017-07-27 | 2017-07-27 | Method for preparing 1, 4-pentanediol by directly hydrogenating levulinic acid by using copper-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107597116B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256198A (en) * | 2019-07-12 | 2019-09-20 | 中国科学院兰州化学物理研究所 | A kind of production method of 1,4- pentanediol |
| CN115536495A (en) * | 2022-10-12 | 2022-12-30 | 河北工业大学 | Method for preparing 1, 4-pentanediol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445426A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Method for preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN102976883A (en) * | 2012-11-26 | 2013-03-20 | 金骄特种新材料（集团）有限公司 | Preparation method of bio-based polyalkyl cyclopentane synthetic oil |
-
2017
- 2017-07-27 CN CN201710621151.2A patent/CN107597116B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445426A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Method for preparing ethylene glycol by using dimethyl oxalate plus hydrogen |
| CN102976883A (en) * | 2012-11-26 | 2013-03-20 | 金骄特种新材料（集团）有限公司 | Preparation method of bio-based polyalkyl cyclopentane synthetic oil |
Non-Patent Citations (1)
| Title |
|---|
| MENGXIA LI, ET AL.: "Aqueous phase hydrogenation of levulinic acid to 1,4-pentanediol", 《CHEMICAL COMMUNICATIONS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256198A (en) * | 2019-07-12 | 2019-09-20 | 中国科学院兰州化学物理研究所 | A kind of production method of 1,4- pentanediol |
| CN115536495A (en) * | 2022-10-12 | 2022-12-30 | 河北工业大学 | Method for preparing 1, 4-pentanediol |
| CN115536495B (en) * | 2022-10-12 | 2023-12-15 | 河北工业大学 | Method for preparing 1, 4-pentanediol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107597116B (en) | 2020-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103785470B (en) | A kind of preparation method for the synthesis of acrylic acid catalyst | |
| CN105903482B (en) | A kind of CoP/TiO2Composite photo-catalyst and its preparation and application | |
| CN101905157A (en) | Method for preparing mercury-free catalyst for preparing chloroethylene by acetylene hydrochlorination | |
| CA2198777C (en) | Photocatalyst, method for preparing the same, and production of hydrogen using the same | |
| CN105367404A (en) | Method for preparing formate through carbon dioxide catalytic hydrogenation | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| CN102442886A (en) | Method for directly preparing glycols from biological cellulosan | |
| CN110624575A (en) | BiOBr/Bi12SiO20Electrochemical preparation method and application of composite film photocatalyst | |
| CN104710282B (en) | Method for producing ethanol co-production methanol | |
| CN101659597A (en) | Method for preparing Guerbet alcohol | |
| CN109896923B (en) | Method for preparing high-carbon primary alcohol by ethanol conversion on bi-component catalyst | |
| CN103657643A (en) | Method for preparing nano palladium metal catalyst | |
| CN101792368A (en) | Method for preparing alpha-phenethyl alcohol | |
| CN107597116A (en) | A kind of method that 1,4 pentanediols are prepared by copper-based catalysts direct hydrogenation levulic acid | |
| CN101961661B (en) | Organo-metallic catalyst for preparing cyclohexane by hydrogenation of benzene and preparation method and application thereof | |
| CN101428222B (en) | Catalyst for producing 1,2-propylene glycol with glycerol hydrogenolysis and preparation method thereof | |
| CN110078702A (en) | A kind of method of poly ion liquid frame catalyst preparation cyclic carbonate | |
| CN109608304A (en) | A kind of method that furfural hydrogenation directly produces 1,2- pentanediol | |
| CN107286006B (en) | Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin | |
| CN102442992A (en) | Method for synthesizing glycerol carbonate with biodiesel based crude glycerine and dimethyl carbonate | |
| CN103360220B (en) | A kind of method of voluminous Resorcinol | |
| CN111116386A (en) | Synthetic method of hydroxyethyl ethylenediamine | |
| CN114602477B (en) | For CO 2 Double-shell hollow copper-zinc-based catalyst for preparing methanol at low temperature and preparation method thereof | |
| CN102372636A (en) | Process for synthesizing dimethyl carbonate by using transesterification process | |
| CN113559864B (en) | Preparation method and application of CuCoCe composite catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |