CN102432445B - Method for preparing dihydroxy acetone by selectively oxidizing glycerin with hydrogen peroxide - Google Patents
Method for preparing dihydroxy acetone by selectively oxidizing glycerin with hydrogen peroxide Download PDFInfo
- Publication number
- CN102432445B CN102432445B CN201110297133.6A CN201110297133A CN102432445B CN 102432445 B CN102432445 B CN 102432445B CN 201110297133 A CN201110297133 A CN 201110297133A CN 102432445 B CN102432445 B CN 102432445B
- Authority
- CN
- China
- Prior art keywords
- solution
- glycerin
- hydrogen peroxide
- catalyst
- mass percent
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing dihydroxy acetone by selectively oxidizing glycerin with hydrogen peroxide and belongs to the field of preparation of the dihydroxy acetone. The method comprises the following steps of: adding a transition metal hydrotalcite-like compound as a catalyst in 10 to 100 mass percent of glycerin aqueous solution, and controlling the dosage of the catalyst to be 5 to 20 percent of the mass of the glycerin; raising the temperature of a mixture to 25 to 90 DEG C by heating, dripping 3 to 50 mass percent of hydrogen peroxide, and reacting for 1 to 24 h; after reaction, centrifugally separating the catalyst from a reaction solution; and recovering the catalyst for reusing, and feeding the reaction solution to a liquid chromatogram for identification analysis. By using the glycerin and the hydrogen peroxide as raw materials, under the action of the transition metal hydrotalcite-like compound which serves as the catalyst, the conversion rate of the glycerin and the yield of the dihydroxy acetone are high; any acid base and any organic additive are not added in a reaction system; and the method has the advantages of high yield, low cost, no environmental pollution, easiness in separation, good repeatability, and the like.
Description
Technical field
The present invention relates to the preparation method of otan, specially refer to a kind of method of utilizing hydrogen peroxide selective oxidation glycerine to prepare otan.
Background technology
Petroleum resources day by day in short supply and constantly aggravating circumstances, force people actively to seek reproducible clean energy and substitute fossil energy, therefore take natural fats and oils, prepares biofuel receive much attention in recent years as raw material.In this process, 1 ton of biofuel of every generation, will produce the by-product glycerin of 100 kg, therefore in the last few years, glycerine output grew with each passing day with the development of Biodiesel, was therefore badly in need of finding new outlet for glycerine.In all multi-usages of glycerine, by the R-Glyceric acid of glycerine oxidation preparation high added value, Glycerose, otan, oxyacetic acids etc. have much market outlook.
Wherein, otan is a kind of important chemical industry, biochemical raw material, medicine, agricultural chemicals synthetic intermediate and polyfunctional food additive, and purposes is very extensive.Seldom, it produces at present or blank out the report of domestic relevant DHA.External method of producing otan is mainly microbial method at present, its mechanism is the glycerol dehydrogenase that utilizes microbial metabolism to produce, make the structural secondary position of a glycerol molecule hydroxyl carry out dehydrogenation reaction generate otan (Process Biochemistry, 1991,26:243-248).Microbe transformation method reaction conditions is gentle, simple to operate, but bacterial classification is expensive, be difficult for storing, and product separation purifying technique is loaded down with trivial details.
Direct Catalytic Oxidation method is under the effect of catalyzer and oxygenant, the method that is otan by transformation of glycerol by single step reaction.Hiroshi Kimura etc. when adopting Pt/C, Pt-Bi/C and Pt-Bi-Ce/C catalyzer, all obtained certain catalytic effect (Appl. Catal., A, 1993,96,217-228.).Composition and the conversion unit of the improved Pt-Bi/C catalyzer such as Wenbin Hu, 48% otan productive rate and 80% glycerol conversion yield (Ind. Eng. Chem. Res. under the acidic conditions of pH=2.1, have been obtained, 2010,49 (21): 10876-10882).But in many reports, the concentration of the glycerine raw material in reaction is all lower, and reaction system will add certain acid or alkali, and to adopt expensive precious metal be catalyzer more.Therefore how to realize and take high density glycerine as raw material, under neutrallty condition, utilize cheap transition-metal catalyst highly selective catalyzed oxidation glycerine, become a current difficult problem urgently to be resolved hurrily.
Summary of the invention
1. the technical problem that invention will solve
For the microbial method of producing otan, bacterial classification is expensive, be difficult for storing, and the problem that product separation purifying technique is loaded down with trivial details and Direct Catalytic Oxidation method exists, the invention provides a kind of method of utilizing hydrogen peroxide selective oxidation glycerine to prepare otan.
2. technical scheme
Utilize hydrogen peroxide selective oxidation glycerine to prepare a method for otan, take glycerine and hydrogen peroxide as raw material, take transition metal houghite as catalyzer, the steps include:
(1) in the aqueous glycerin solution that is 10～100% at mass percent concentration, adding transition metal houghite is catalyzer, and to control catalyst levels be qualities of glycerin 5～20%;
(2) above-mentioned steps (1) mixture is heated to 25～90 ℃, then drips mass percent concentration and be 3～50% hydrogen peroxide, react 1～24 h;
(3) reaction after by catalyzer and reaction solution centrifugation, catalyst recovery is reused, reaction solution is delivered to liquid chromatography identification and analysis.
Utilize hydrogen peroxide selective oxidation glycerine to prepare the catalyzer described in the method for otan, its preparation method is:
(1) mixed aqueous solution of preparation divalent transition metal nitrate and aluminum nitrate, controls divalent metal and aluminum ions mol ratio 2.0～5.0; Control cationic total concn at 0.2～1.5 mol/L;
(2) preparation aqueous sodium carbonate, the mole dosage of controlling sodium carbonate and aluminum nitrate is identical, after being mixed, fully stir 0.5 hour above two solution, temperature is controlled at 60 ℃, in this process, utilize the pH value of NaOH control mixing solutions 9.0 ~ 11.5, then the colloid of gained is filtered or centrifuge dehydration, wash with water to neutrality, 100 ℃ of oven dry, N at 300～700 ℃ of the solid samples of gained
2in gas, calcine 2 hours, can obtain corresponding composite oxide of metal;
(3) composite oxide of metal being placed in to mass percent concentration is 10 ~ 50% aqueous glycerin solution, pH value is controlled at 9.0 ~ 11.5, temperature is controlled at 60～100 ℃ and stirs 24 hours, the colloid of gained filters or centrifuge dehydration, 100 ℃ of oven dry, both required transition metal-type hydrotalcite catalyst.
Described transition metal is one or more in Cr, Mn, Fe, Co, Ni, Cu.
Product analysis: deliver to after reaction product centrifuging on Agilent1200 type high performance liquid chromatograph and analyze by external standard method.Chromatographic condition is as follows: Aminex HPX-87H chromatographic column (Bio-Rad, 300 * 7.8mm), 60 ℃ of column temperatures, 0.01mol/L H
2sO
4moving phase, flow velocity 0.5 mL/min, ultraviolet and differential detector, ultraviolet detection wavelength 210 nm, sample size 10 μ L.
3. beneficial effect
The present invention compared with prior art tool has the following advantages:
(1) method for preparing catalyst is simple, easy to operate, pollutes lowly, and reusability is good;
(2), in the oxidizing reaction of glycerine, the transformation efficiency of glycerine and the yield of otan are high;
(3) reaction conditions is gentle, does not add any soda acid and organic additive in reaction system, environment is not produced and polluted, and target product is easily separated.
Embodiment
Embodiment 1
By 8.61 kg Mn (NO
3)
26H
2o and 3.75 kg Al (NO
3)
39H
2o is made into 120 L solution with deionized water; By 1.06 kg Na
2cO
3with deionized water, be made into 120 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 10.5.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 500 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 10% in mass percent concentration, pH value is controlled at 10.5,60 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 10% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 10%, is warming up to after 60 ℃, starts to drip mass percent concentration and be 3.0% hydrogen peroxide, react after 6 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
Embodiment 2
By 4.04 kg Fe (NO
3)
29H
2o, 2.91 kg Co (NO
3)
26H
2o and 3.75kg Al (NO
3)
39H
2o is made into 20 L solution with deionized water; By 1.06 kg Na
2cO
3with deionized water, be made into 20 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 9.0.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 300 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 10% in mass percent concentration, pH value is controlled at 9.0,60 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 10% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 10%, is warming up to after 70 ℃, starts to drip mass percent concentration and be 3.0% hydrogen peroxide, react after 6 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
Embodiment 3
By 4.00 kg Cr (NO
3)
29H
2o, 2.42 kg Cu (NO
3)
23H
2o, 2.83 kg Mn (NO
3)
26H
2o, 5.82 kg Ni (NO
3)
26H
2o and 3.75 kg Al (NO
3)
39H
2o is made into 300 L solution with deionized water; By 1.06 kg Na
2cO
3with deionized water, be made into 300 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 10.0.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 700 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 50% in mass percent concentration, pH value is controlled at 10.0,60 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 10% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 10%, is warming up to after 60 ℃, starts to drip mass percent concentration and be 3.0% hydrogen peroxide, react after 6 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
Embodiment 4
By 2.42 kg Cu (NO
3)
23H
2o, 5.82 kg Ni (NO
3)
26H
2o and 3.75 kg Al (NO
3)
39H
2o is made into 40 L solution with deionized water; By 1.06 kg Na
2cO
3with deionized water, be made into 40 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 10.0.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 500 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 40% in mass percent concentration, pH value is controlled at 10.0,80 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 40% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 20%, be warming up to after 50 ℃, start to drip mass percent concentration and be 3.0% hydrogen peroxide, react after 24 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
Embodiment 5
By 0.48 kg Cu (NO
3)
23H
2o, 11.32 kg Fe (NO
3)
29H
2o and 3.75 kg Al (NO
3)
39H
2o is made into 40 L solution with deionized water; By 1.06 kg Na
2cO
3with deionized water, be made into 40 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 11.5.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 650 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 30% in mass percent concentration, pH value is controlled at 11.5,100 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 80% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 20%, is warming up to after 60 ℃, starts to drip mass percent concentration and be 10% hydrogen peroxide, react after 12 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
Embodiment 6
By 9.04 kg Mn (NO
3)
24H
2o, 1.62 kg Fe (NO
3)
29H
2o and 7.50 kg Al (NO
3)
39H
2o is made into 100 L solution with deionized water; By 2.12 kg Na
2cO
3with deionized water, be made into 100 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 10.0.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 450 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 20% in mass percent concentration, pH value is controlled at 10.0,60 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 100% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 20%, be warming up to after 60 ℃, start to drip mass percent concentration and be 30% hydrogen peroxide, react after 12 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
Embodiment 7
By 10.04 kg Mn (NO
3)
24H
2o, 0.24 kg Cu (NO
3)
23H
2o and 7.50 kg Al (NO
3)
39H
2o is made into 80 L solution with deionized water; By 2.12 kg Na
2cO
3with deionized water, be made into 80 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 10.0.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 550 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 50% in mass percent concentration, pH value is controlled at 10.0,60 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 100% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 20%, be warming up to after 90 ℃, start to drip mass percent concentration and be 20% hydrogen peroxide, react after 18 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
Embodiment 8:
By 5.02 kg Mn (NO
3)
24H
2o, 11.32 kg Co (NO
3)
26H
2o and 7.50 kg Al (NO
3)
39H
2o is made into 80 L solution with deionized water; By 2.12 kg Na
2cO
3with deionized water, be made into 80 L solution, after two solution mix, vigorous stirring is 0.5 hour at 60 ℃, and adding NaOH, to control mixed liquid pH value be 10.0.The colloid of gained filters or centrifuge dehydration, is washed to neutrality, after 100 ℃ of oven dry, is placed in N at 350 ℃
2in atmosphere, calcine 2 hours, in the aqueous glycerin solution that gained sample is 20% in mass percent concentration, pH value is controlled at 10.0,60 ℃ and stirs 24 hours, and gained colloid filters or centrifuge dehydration, 100 ℃ of oven dry, both required catalyzer.Get mass percent concentration and be 100% aqueous glycerin solution 5 L, the institute's controlling catalyst that adds qualities of glycerin 5.0%, be warming up to after 25 ℃, start to drip mass percent concentration and be 50% hydrogen peroxide, react after 1 h catalyzer and reaction solution centrifugation, reaction solution is delivered to liquid chromatography identification and analysis.The results are shown in Table 1.
The result cartogram of table 1 embodiment 1 ~ 8
| Embodiment | Glycerol conversion yield (%) | Otan selectivity (%) |
| Embodiment 1 | 13.3 | 33.5 |
| Embodiment 2 | 45.4 | 23.0 |
| Embodiment 3 | 52.6 | 34.9 |
| Embodiment 4 | 100.0 | 24.2 |
| Embodiment 5 | 80.4 | 74.6 |
| Embodiment 6 | 70.5 | 36.4 |
| Embodiment 7 | 90.4 | 31.8 |
| Embodiment 8 | 18.9 | 85.7 |
Claims (1)
1. utilize hydrogen peroxide selective oxidation glycerine to prepare a method for otan, the steps include:
(1) in the aqueous glycerin solution that is 10～100% at mass percent concentration, adding transition metal houghite is catalyzer, and to control catalyst levels be qualities of glycerin 5～20%;
(2) above-mentioned steps (1) mixture is heated to 25～90 ℃, then drips mass percent concentration and be 3～50% hydrogen peroxide, react 1～24 h;
(3) reaction after by catalyzer and reaction solution centrifugation, catalyst recovery is reused, reaction solution is delivered to liquid chromatography identification and analysis; Catalyzer its preparation method described in step (1) is: the mixed aqueous solution of preparation divalent transition metal nitrate and aluminum nitrate, control divalent metal and aluminum ions mol ratio 2.0～5.0; Control cationic total concn at 0.2～1.5 mol/L; Preparation aqueous sodium carbonate, the mole dosage of controlling sodium carbonate and aluminum nitrate is identical, after being mixed, fully stir 0.5 hour above two solution, temperature is controlled at 60 ℃, in this process, utilize the pH value of NaOH control mixing solutions 9 ~ 11.5, then the colloid of gained is filtered or centrifuge dehydration, wash with water to neutrality, 100 ℃ of oven dry, N at 300～700 ℃ of the solid samples of gained
2in gas, calcine 2 hours, can obtain corresponding composite oxide of metal; It is 10 ~ 50% aqueous glycerin solution that composite oxide of metal is placed in to mass percent concentration, pH value is controlled at 9 ~ 11.5, and temperature is controlled at 60～100 ℃ and stirs 24 hours, and the colloid of gained filters or centrifuge dehydration, 100 ℃ of oven dry, both required transition metal-type hydrotalcite catalyst; Described transition metal is one or more in Cr, Mn, Fe, Co, Ni, Cu.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110297133.6A CN102432445B (en) | 2011-09-30 | 2011-09-30 | Method for preparing dihydroxy acetone by selectively oxidizing glycerin with hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110297133.6A CN102432445B (en) | 2011-09-30 | 2011-09-30 | Method for preparing dihydroxy acetone by selectively oxidizing glycerin with hydrogen peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102432445A CN102432445A (en) | 2012-05-02 |
| CN102432445B true CN102432445B (en) | 2014-03-12 |
Family
ID=45980841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110297133.6A Active CN102432445B (en) | 2011-09-30 | 2011-09-30 | Method for preparing dihydroxy acetone by selectively oxidizing glycerin with hydrogen peroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102432445B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321360A (en) * | 2017-06-20 | 2017-11-07 | 南京工程学院 | It is a kind of to prepare bismuth-containing catalysts of glyceric acid and preparation method thereof for selective oxidation glycerine |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274911B (en) * | 2013-05-09 | 2015-04-15 | 浙江金伯士药业有限公司 | Novel preparation method of 1,3-dihydroxyl-2-acetone |
| CN109400461A (en) * | 2018-09-17 | 2019-03-01 | 南京工程学院 | The method and its application of hydrogen peroxide catalyzed glycerol |
| CN109499581B (en) * | 2018-12-22 | 2021-11-30 | 江西师范大学 | Catalyst for preparing 1, 3-dihydroxyacetone from glycerol and preparation method thereof |
| CN115445611B (en) * | 2022-09-23 | 2024-01-26 | 北京化工大学 | Catalyst for preparing dihydroxyacetone by selective oxidation of glycerol and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279902A (en) * | 2008-05-23 | 2008-10-08 | 浙江大学 | One-step method for preparing dihydroxy acetone by dioxygen catalytic oxidation of glycerol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009137891A (en) * | 2007-12-06 | 2009-06-25 | Lion Corp | Method for producing dihydroxyacetone or glycolic acid |
-
2011
- 2011-09-30 CN CN201110297133.6A patent/CN102432445B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279902A (en) * | 2008-05-23 | 2008-10-08 | 浙江大学 | One-step method for preparing dihydroxy acetone by dioxygen catalytic oxidation of glycerol |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2009-137891A 2009.06.25 |
| 纪红兵等.水滑石类材料应用于氧化反应研究最新进展.《天然气化工》.2002,第27卷(第1期),49-55转61. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321360A (en) * | 2017-06-20 | 2017-11-07 | 南京工程学院 | It is a kind of to prepare bismuth-containing catalysts of glyceric acid and preparation method thereof for selective oxidation glycerine |
| CN107321360B (en) * | 2017-06-20 | 2019-11-08 | 南京工程学院 | A kind of bismuth-containing catalysts and preparation method thereof preparing glyceric acid for selective oxidation glycerol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432445A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432445B (en) | Method for preparing dihydroxy acetone by selectively oxidizing glycerin with hydrogen peroxide | |
| Qiu et al. | High-efficient preparation of gasoline-ranged C5–C6 alkanes from biomass-derived sugar polyols of sorbitol over Ru-MoO3− x/C catalyst | |
| CN105315130B (en) | A kind of method that 1,3 dihydric alcohols are prepared by Prins condensation reactions | |
| CN101695657B (en) | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin | |
| CN108586181B (en) | Method for decarbonylating grease into long-chain alkane under hydrogen-free condition | |
| CN107250086A (en) | Ethanol is converted into the lower hydrocarbon of functionalization and the method for downstream hydrocarbon | |
| CN105218289B (en) | A kind of method that unrighted acid original position hydrogenation decarboxylation prepares long chain alkane | |
| CN105712840A (en) | Method for producing high-carbon primary alcohols by catalytic conversion of ethanol | |
| Kutálek et al. | Aspects of Mg–Al mixed oxide activity in transesterification of rapeseed oil in a fixed-bed reactor | |
| CN107537533B (en) | Catalyst and its process for Oxidative Dehydrogenation of Butene into Butadiene under low-water ratio conditions | |
| Tong et al. | Efficient and selective transformation of biomass-derived furfural with aliphatic alcohols catalyzed by a binary Cu-Ce oxide | |
| Jiménez-Morales et al. | Preparation of stable sulfated zirconia by thermal activation from a zirconium doped mesoporous MCM-41 silica: Application to the esterification of oleic acid with methanol | |
| Park et al. | Catalytic decomposition of 4-phenoxyphenol to aromatics over palladium catalysts supported on activated carbon aerogel bearing sulfonic acid group | |
| CN103933961A (en) | Catalyst for synthesizing propylene carbonate as well as preparation method and application of catalyst | |
| CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
| US12071400B2 (en) | Process of selective oxidation of glycerol | |
| Zhang et al. | Synthesis of nitriles from allyl alcohol derived from glycerol over a bimetallic catalyst Zn30Ru1. 0/γ-Al2O3 | |
| CN102389800A (en) | Catalyst for use in preparation of 1,2-propanediol by low-temperature low-pressure hydrogenation of biological glycerol and preparation method thereof | |
| CN104311404A (en) | Method for producing cinnamyl aldehyde | |
| CN106431843B (en) | A kind of method that ecological oil prepares phenolic compound | |
| CN109422638A (en) | ABE fermentation liquid conversion prepares ketone compounds method | |
| CN107537530A (en) | Catalyst and its process for Oxidative Dehydrogenation of Butene into Butadiene | |
| CN102659572A (en) | Preparation method of dehydroabietic acid | |
| CN108002994A (en) | A kind of method for preparing high-carbon ketone | |
| Zhu et al. | Manganese carbonate-zinc glycerolate, synthesis, characterization and application as catalyst for transesterification of soybean oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wu Gongde Inventor after: Wang Xiaoli Inventor after: Wang Huiya Inventor after: Ding Keqiang Inventor after: Zhang Fang Inventor after: Liu Xianfeng Inventor after: Sun Wen Inventor after: Song Xiaobo Inventor before: Wu Gongde Inventor before: Wang Xiaoli Inventor before: Ding Keqiang Inventor before: Zhang Fang Inventor before: Liu Xianfeng Inventor before: Sun Wen Inventor before: Song Xiaobo |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: WU GONGDE WANG XIAOLI DING KEQIANG ZHANG FANG LIU XIANFENG SUN WEN SONG XIAOBO TO: WU GONGDE WANG XIAOLI WANG HUIYA DING KEQIANG ZHANG FANG LIU XIANFENG SUN WEN SONG XIAOBO |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |