CN105061140A - Method for preparing fatty alcohol from fatty acid or fatty acid ester under H-free condition and catalyst applied to method - Google Patents
Method for preparing fatty alcohol from fatty acid or fatty acid ester under H-free condition and catalyst applied to method Download PDFInfo
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- CN105061140A CN105061140A CN201510489009.8A CN201510489009A CN105061140A CN 105061140 A CN105061140 A CN 105061140A CN 201510489009 A CN201510489009 A CN 201510489009A CN 105061140 A CN105061140 A CN 105061140A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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Abstract
The invention discloses a method for preparing fatty alcohol from fatty acid or fatty acid ester under an H-free condition. According to the method, under the H-free condition, the fatty acid or fatty acid ester is taken as the raw material, H2 is generated in situ by a solvent, and the fatty acid or fatty acid ester is selectively converted into corresponding fatty alcohol by a supported Cu-based or Ni-based catalyst under a mild condition. H is not needed to be added externally to realize selective hydrogenation of the fatty acid or fatty acid ester, the conversion rate of the raw material is higher than 95%, and the selectivity of the fatty alcohol is higher than 99%. The method is safe and green, has the advantages of high conversion rate, high selectivity, good catalytic system circulation, simple process, high operability and the like, is suitable for industrialized scale production and has broad application prospects.
Description
Technical field
The present invention relates to grease transformation technology field, be specifically related to lipid acid or fatty acid ester selective hydrogenation under a kind of hydrogen-free condition and prepare the method for fatty alcohol, and be applied to the load type metal catalyst that lipid acid or fatty acid ester selective hydrogenation prepare fatty alcohol.
Background technology
Fatty alcohol is as a kind of basic chemical industry raw material, and consumption is large and added value is high, has important effect in national economy.The fine chemical product huge number produced by it, is widely used in the fields such as food, medical and health, weaving, papermaking, building, machinery, communications and transportation.And the mixture of the high fatty alcohol straight-chain monohydric alcohol that to be carbon atom quantity many, mainly make various esters product, as the polymeric plasticizer such as rubber, plastics, be also used as washing composition.
Fatty alcohol is produced from spermaceti the earliest, and the production method of modern fatty alcohol is divided into natural fats and oils preparation method and synthesis method.The fatty alcohol that the former produces is called natural fatty alcohol, and the latter is that the fatty alcohol that raw material generates is called synthetic fatty alcohol with petroleum products.Natural fatty alcohol, because of the feature that its quality product is high, environmental friendliness, sustainability are strong, is obviously better than synthetic fatty alcohol, meets the concept of Green Chemistry, thus becomes main flow production method.Natural fats and oils preparation method mainly contains aliphatic acid hydrogenation preparation method, fatty acid methyl ester hydrogenation preparation method.Natural fats and oils hydrolysis is obtained lipid acid by the former, more direct to aliphatic acid hydrogenation, and the method condition is harsher.What current employing was more is the latter's fatty acid methyl ester hydrogenation method, by methyl alcohol and grease generation transesterification permutoid reaction, generate fatty acid methyl ester, then Hydrogenation obtains saturated fatty alcohol under catalyst action.
CN102476056A discloses a kind of catalyzer for fatty acid methyl ester shortening fatty alcohol, by cupric oxide or cupric oxide and zinc oxide mix, one in manganese oxide, nickel oxide or two kinds, aluminum oxide and carrier composition, carrier is diatomite or calcium carbonate; Also disclose a kind of preparation method of the catalyzer for fatty acid methyl ester shortening fatty alcohol.But this invention needs to be filled with a large amount of hydrogen, and reaction pressure is higher, reaches 10MPa.CN102807470A discloses a kind of preparation method of high fatty alcohol, comprising and grease and methyl alcohol are generated Fatty acid methyl ester by transesterification, fatty acid methyl ester hydrogenation generated the step of high fatty alcohol, being also included in the step by first using urea adduct method separation and purification before fatty acid methyl ester hydrogenation.The method selectivity and transformation efficiency are obtained for raising, all can reach more than 80%, but many this steps of urea adduct method separation and purification, and this step is more complicated.CN103965016A discloses the method that fatty acid methyl ester hydrogenation under a kind of temperature control catalyst system prepares fatty alcohol, it is characterized in that adopting the imidazolyl temperature control particle liquid stabilising Pd nano metal particles containing different lengths Soxylat A 25-7 segment to be catalyzer, in fatty acid methyl ester, temperature controlled ionic liquid catalyst system, hydrogen atmosphere, catalyze fatty acid methyl ester hydrogenation prepares fatty alcohol, and to containing temperature control particle liquid catalyst systems Separation and Recovery and the recycle of Pd nano metal particles.It is good that this invention catalyst system recycles performance, but temperature controlled ionic liquid preparation method used is complicated, and influence factor is many, is not easy to control, catalyzer poor reproducibility.USP5124491 discloses a kind of Cu-Cr-Mn-Si-Ba catalyzer, and it is active that this catalyzer has higher fatty acid methyl ester hydrogenation, but selectivity is lower, and the highest only have 85.6wt%.
At present, industrial main employing Cu-Cr catalyst preparing fatty alcohol, but the Cr that Cu-Cr catalyzer discharges in preparation process
6+serious pollution is caused to environment, therefore recently research mainly concentrates on the new auxiliary agent of exploitation and carrys out alternative Cr element, as Cu-Mn series catalysts, Cu-Zn series catalysts and Cu-Fe series catalysts emerge successively, these catalyzer have excellent performance in catalytic activity, selectivity and life-span etc., but still can not solve the higher problem of reaction pressure in catalytic hydrogenation well.And there is severe reaction conditions, selectivity and transformation efficiency and be difficult to some shortcomings such as unified, reaction process is complicated in other catalyzer.
What industrial employing was more is fatty acid methyl ester hydrogenation method: by methyl alcohol and grease generation transesterification permutoid reaction, generate fatty acid methyl ester, then Hydrogenation obtains saturated fatty alcohol under catalyst action.These class methods need added hydrogen, and lack the response path directly transformed grease.
Summary of the invention
For the deficiency that existing fatty alcohol preparation technology exists, the invention provides a kind of green safety, technique is simple, without the need to added hydrogen, and do not need transesterify pre-treatment, utilize the catalyst based method that directly lipid acid or fatty acid ester selective hydrogenation can be converted into corresponding saturated fatty alcohol of Cu or Ni, and realize high conversion and highly selective.
The present invention prepares the method for fatty alcohol by lipid acid under hydrogen-free condition or fatty acid ester selective hydrogenation, raw fatty acid or fatty acid ester, hydrogen supply dissolvent, loading type Cu or Ni based metal catalysts are added in reactor, under hydrogen-free condition, be warming up to temperature of reaction 150-300 DEG C, sustained reaction 0.1-36h, obtained product fatty alcohol; Wherein, described load type metal catalyst comprises Cu or Ni metal center and carrier.
In the inventive method, described raw fatty acid or fatty acid ester comprise in Vegetable oil lipoprotein containing lipid acid and/or fatty acid ester, animal grease, compound lard one or more; Wherein, described lipid acid is that straight chain is saturated, undersaturated aliphatic acid, preferred C
10-C
20linear saturated fatty acids, comprise capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid; Described fatty acid ester comprises Fatty acid methyl ester, fatty acid ethyl ester, glycerol fatty acid ester etc.; Described animal grease containing lipid acid and/or fatty acid ester or Vegetable oil lipoprotein or compound lard comprise Oleum Cocois, plam oil, algal oil, trench wet goods.
In the inventive method, described hydrogen supply dissolvent comprise alcohols, acids, fat hydrocarbon, naphthenic hydrocarbon, alkene one or more.Be preferably alcohols, fat hydrocarbon and alkene.
In the inventive method, described catalyzer is load type metal catalyst.Wherein, described metal is Cu or Ni, and described carrier is no acidic carrier, comprises one or more in molecular sieve, oxide compound, gac, amorphous silicon aluminium, one or more in preferred silicon-dioxide, zirconium dioxide, gac, pure silicon molecular sieve;
In the inventive method, the mass ratio of described loaded catalyst and described raw fatty acid or fatty acid ester is 1:1-100.
In the inventive method, described hydrogen-free condition to refer to before reaction not added hydrogen.Described temperature of reaction is 150-300 DEG C.The described reaction times is 0.1-36h.
In the inventive method, described reactor is batch reactor, paste state bed reactor or fixed-bed reactor.
In the inventive method, described product is the saturated fatty alcohol corresponding with raw fatty acid or fatty acid ester; The transformation efficiency of described reaction reaches more than 95%; The selectivity of described product fatty alcohol is up to 99%, and described reaction is such as formula shown in (I):
Wherein, R
1c
10-C
20alkyl, R
2c
1-C
3alkyl.
The invention allows for a kind of loading type Cu or Ni metal catalyst, comprise Cu or Ni metal center and carrier, the loading of described loaded catalyst is 1-100%.In hydrogen supply dissolvent, lipid acid or fatty acid ester selective hydrogenation are prepared corresponding fatty alcohol under its role is to hydrogen-free condition.
Load type metal catalyst of the present invention comprises Cu/SBA-15, Cu/SiO
2, Ni/SiO
2, Ni/C, Ni/SBA-15, Cu/ diatomite, Ni/ diatomite etc.
In load type metal catalyst of the present invention, described carrier is no acidic carrier, comprises one or more in molecular sieve, oxide compound, gac, amorphous silicon aluminium, is preferably one or more in silicon-dioxide, zirconium dioxide, pure silicon molecular sieve.
The preparation method of load type metal catalyst of the present invention is the known precipitator method, pickling process, thermal decomposition method, scorification, reduction method.For Cu/SBA-15, prepare via the precipitator method: under 70 DEG C of agitation conditions, cupric nitrate is dissolved in deionized water, dropwise adds urea, add SBA-15,90 DEG C of reflux condensation mode heating 10h, suction filtration, dries, air calcination, hydrogen reducing, obtains Catalysts Cu/SBA-15.
Prepare the novel method of fatty alcohol under the present invention proposes a kind of hydrogen-free condition, namely with lipid acid or fatty acid ester for raw material, produce H by hydrogen supply dissolvent original position
2, in a mild condition by load type metal catalyst catalysis, by selective hydrogenation process, selective conversion lipid acid or fatty acid ester generate corresponding fatty alcohol.
Beneficial effect of the present invention is:
The fatty acid methyl ester hydrogenation method that current industrial employing is more, all first methyl alcohol and grease reaction will be generated fatty acid methyl ester, then Hydrogenation obtains saturated fatty alcohol under catalyst action.And the present invention proposes new response path, can realize grease direct hydrogenation prepares fatty alcohol, without the need to experiencing transesterification reaction, saves equipment investment and energy loss.Compare current Hydrogenation all to need to be filled with a large amount of hydrogen for the technology of fatty alcohol, power consumption is serious, and hypertonia at the reaction temperatures, there is potential safety hazard, the present invention is without the need to added hydrogen, by hydrogen supply dissolvent (alcohols, acids, fat hydrocarbon, naphthenic hydrocarbon, alkene one or more), for reaction system provides hydrogen, technique is simple and safe, environmental protection.The Cr discharged in fatty alcohol technology used catalyst preparation process is prepared in existing industry
6+cause serious environmental pollution, and there is severe reaction conditions, selectivity and transformation efficiency and be difficult to some shortcomings such as unified, reaction process is complicated.The present invention avoids using Cr element, and with Cu or Ni for monometallic Center catalyzer, react in a mild condition, feed stock conversion more than 95%, the selectivity of product fatty alcohol reaches 99%.The adaptability of the present invention to glyceride stock is high, can transform Oleum Cocois, plam oil, algal oil, trench wet goods.The inventive method safe green, has the advantages such as transformation efficiency is high, selectivity is high, catalyst system cyclicity is good, technique is simple, workable, is suitable for commercial scale production, is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 represents the scanning electron microscope (SEM) photograph of the load type metal catalyst of preparation in embodiment 1.
Fig. 2 represents the transmission electron microscope picture of the load type metal catalyst of preparation in embodiment 1.
Fig. 3 represents the color atlas of the liquid product that method prepares in embodiment 2.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
Embodiment 1
For Catalysts Cu/SBA-15 conventional in the present invention, prepare via the precipitator method: under agitation, 3g cupric nitrate is dissolved in 250mL deionized water, dropwise adds 6g urea after being warming up to 70 DEG C, then add 2gSBA-15,90 DEG C of reflux condensation mode heating 10h, suction filtration, dries, with the air atmosphere 400 DEG C of 100mL/min calcining 4h, again with the hydrogen atmosphere 400 DEG C of 100mL/min reduction 4h, obtain Catalysts Cu/SBA-15.The loading 29% of Ni metal in the catalyzer measured through ICP listed by table 1, and by the specific surface area 857m of nitrogen adsorption assay catalyzer
2g
-1with pore volume 0.76cm
3g
-1.Fig. 1 is Catalysts Cu/SBA-15 scanning electron microscope (SEM) photograph, analyzes the size obtaining carrier and is about 15 ± 5nm.Fig. 2 is Catalysts Cu/SBA-15 transmission electron microscope picture, analyzes the size obtaining Cu metallics and is about 5nm.The Main physical character of the catalyzer in the present embodiment and in following embodiment is in table 1.
The Main physical character of table 1 catalyzer
Embodiment 2
In order to study the dehydrogenation of the hydrogen supply dissolvent selected in the present invention, dehydrogenation test is carried out to hydrogen supply dissolvent.For ethanol, by Catalysts Cu obtained in 40mL ethanol, 0.2g embodiment 1/SBA-15 mixing adds in reactor, is filled with 1MPa nitrogen after washing still with nitrogen, be warming up to 200 DEG C of reaction 2h, recording manometer registration.Reaction terminates, and after kettle is cooled to room temperature, collects gas-phase product, filtering separation liquid phase and catalyzer.Carry out gas chromatographic detection to gas-phase product, gas-phase product distribution is in table 2.From data analysis, at the temperature of hydrogen-free condition and setting, hydrogen supply dissolvent ethanol generates a large amount of H
2, a small amount of CO, trace CO
2, CH
4.
Gas-phase product distribution (unit: ppm) of table 2 Catalysts Cu/SBA-15 catalyzed conversion ethanol
Embodiment 3
Used catalyst Ni/SiO in the present embodiment
2, the loading 98% of W metal in the catalyzer measured through ICP listed by table 1, and by the specific surface area 241m of nitrogen adsorption assay catalyzer
2g
-1with pore volume 0.43cm
3g
-1.The preparation method of this catalyzer is excessive pickling process, namely takes 9.8g nickelous nitrate, is dissolved in 30mL deionized water, is added drop-wise to 2gSiO
2in, stirred at ambient temperature is complete to moisture evaporation, with the air atmosphere 650 DEG C of 100mL/min calcining 4h, then with the hydrogen atmosphere 650 DEG C of 100mL/min reduction 4h, obtains catalyst n i/SiO
2.
By 20g stearic acid, 1g catalyst n i/SiO
2, 80mL dodecane adds in reactor, is filled with 1MPa nitrogen after washing still with nitrogen, is warming up to 220 DEG C of reaction 4h, recording manometer registration.
Reaction process is carried out according to following reaction formula (II), and stearic acid selective hydrogenation generates corresponding stearyl alcohol.
Reaction terminates, and after kettle is cooled to room temperature, filtering separation liquid product and catalyzer, carry out MS qualitative detection and GC detection by quantitative to liquid product.GC-MS device information: ShimadzuQP-2010Ultra; Chromatographic column information: Rtx-5SilMS (30m × 0.25mm × 0.25 μm).GC program setting: keep 20 minutes after 100 DEG C 10 DEG C/min are warmed up to 280 DEG C.Liquid product distribution is as shown in table 3, and the transformation efficiency of raw material reaches 98.24%, and the selectivity of stearyl alcohol reaches 99.22%.
In the process preparing fatty alcohol, other condition is constant, when the temperature of reacting is within the scope of 150-220 DEG C, all can reach same technique effect.
In the process preparing fatty alcohol, other condition is constant, when react time at 0.1-4h time, all can reach same technique effect.
Table 3 catalyst n i/SiO
2the selectivity (%) of the stearic liquid product of shortening
Embodiment 4
Used catalyst Ni/ diatomite in the present embodiment, the loading 32% of W metal in the catalyzer measured through ICP listed by table 1, and by the specific surface area 55m of nitrogen adsorption assay catalyzer
2g
-1with pore volume 0.65cm
3g
-1.The preparation method of this catalyzer is excessive pickling process, namely 3g nickelous nitrate is taken, be dissolved in 20mL deionized water, be added drop-wise in 2g diatomite, stirred at ambient temperature is complete to moisture evaporation, with the air atmosphere 550 DEG C of 100mL/min calcining 4h, then with the hydrogen atmosphere 550 DEG C of 100mL/min reduction 4h, obtain catalyst n i/ diatomite.
5g methyl palmitate, 1g catalyst n i/ diatomite, 80mL dodecane are added in reactor, after washing still with nitrogen, is filled with 1MPa nitrogen, be warming up to 200 DEG C of reaction 8h, recording manometer registration.
Reaction process is carried out according to following reaction formula (III), and methyl palmitate selective hydrogenation generates corresponding hexadecanol.
Reaction terminates, and after kettle is cooled to room temperature, filtering separation liquid product and catalyzer, carry out MS qualitative detection and GC detection by quantitative to liquid product.Liquid product distribution is as shown in table 4, and the transformation efficiency of raw material reaches 97.12%, and the selectivity of hexadecanol reaches 99.67%.
In the process preparing fatty alcohol, other condition is constant, when scope at 1-5g of the content of raw material methyl palmitate, all can reach same technique effect.
The selectivity (%) of the liquid product of table 4 catalyst n i/ diatomite shortening methyl palmitate
Embodiment 5
Used catalyst Ni/C in the present embodiment, the loading 30% of W metal in the catalyzer measured through ICP listed by table 1, and by the specific surface area 643m of nitrogen adsorption assay catalyzer
2g
-1with pore volume 0.37cm
3g
-1.This catalyzer is prepared via the precipitator method: under agitation, 0.9g nickelous nitrate is dissolved in 250mL deionized water, 6g urea is dropwise added after being warming up to 70 DEG C, add 2g gac again, 90 DEG C of reflux condensation mode heating 10h, suction filtration, dry, with the air atmosphere 550 DEG C of 100mL/min calcining 4h, then with the hydrogen atmosphere 550 DEG C of 100mL/min reduction 4h, obtain catalyst n i/C.
100g Oleum Cocois, 1g catalyst n i/C, 80mL dodecane are added in reactor, after washing still with nitrogen, is filled with 1MPa nitrogen, be warming up to 300 DEG C of reaction 36h, recording manometer registration.Reaction terminates, and after kettle is cooled to room temperature, filtering separation liquid product and catalyzer, carry out MS qualitative detection and GC detection by quantitative to liquid product.Liquid product distribution is as shown in table 5, and the transformation efficiency of raw material reaches 100%, and the selectivity of alcohols reaches 99.76%.
In the process preparing fatty alcohol, other condition is constant, when hydrogen supply dissolvent used be fat hydrocarbon or naphthenic hydrocarbon time, also can reach same technique effect.
The selectivity (%) of the liquid product of table 5 catalyst n i/C shortening Oleum Cocois
Claims (9)
1. under a hydrogen-free condition, lipid acid or fatty acid ester prepare the method for fatty alcohol, it is characterized in that, described method is: add in reactor by raw fatty acid or fatty acid ester, hydrogen supply dissolvent, load type metal catalyst, under hydrogen-free condition, be warming up to temperature of reaction 150-300 DEG C, sustained reaction 0.1-36h, obtains described fatty alcohol; Described metal catalyst comprises carrier and metal center Cu or Ni.
2. the method for claim 1, is characterized in that, described raw material be lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, Fatty acid methyl ester, fatty acid ethyl ester, glycerol fatty acid ester arbitrary one or more.
3. the method for claim 1, is characterized in that, described hydrogen supply dissolvent be alcohols, acids, fat hydrocarbon, naphthenic hydrocarbon, alkene arbitrary one or more.
4. the method for claim 1, is characterized in that, the consumption of described raw material accounts for the mass percent 50-90% of whole reaction system, and the mass percent that the consumption of described hydrogen supply dissolvent accounts for whole reaction system is 10-50%.
5. the method for claim 1, is characterized in that, the carrier of described metal catalyst is no acidic carrier, comprises one or more in molecular sieve, oxide compound, gac, amorphous silicon aluminium.
6. the method for claim 1, is characterized in that, the loading of described loaded catalyst is 1-100%.
7. the method for claim 1, is characterized in that, the mass ratio of described loaded catalyst and raw fatty acid or fatty acid ester is 1:1-100.
8. a load type metal catalyst, is characterized in that, described load type metal catalyst comprises Cu or Ni metal center and carrier; The loading of described loaded catalyst is 1-100%.
9. under load type metal catalyst according to claim 8 being applied to hydrogen-free condition, prepare fatty alcohol by lipid acid or fatty acid ester.
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Cited By (7)
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|---|---|---|---|---|
| CN105777488A (en) * | 2016-03-29 | 2016-07-20 | 青岛科技大学 | Method for catalytically preparing fatty alcohol |
| CN107417494A (en) * | 2017-05-11 | 2017-12-01 | 浙江大学 | The method that a kind of aliphatic acid original position hydrogenation prepares fatty alcohol |
| CN108383685A (en) * | 2018-04-08 | 2018-08-10 | 浙江工业大学 | A kind of method that the conversion of stearic acid hydrogenation deoxidation prepares octadecyl alcolol |
| CN109232185A (en) * | 2018-08-31 | 2019-01-18 | 华东师范大学 | One kettle way conversion dimethyl oxalate is the method for ethylene glycol under a kind of hydrogen-free condition |
| CN111320527A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Non-hydroconversion method of fatty acid |
| CN112221501A (en) * | 2020-11-10 | 2021-01-15 | 西华大学 | Hydrogenation catalyst, preparation method thereof and method for preparing fatty alcohol by catalysis |
| CN113874110A (en) * | 2019-06-28 | 2021-12-31 | 韩华思路信株式会社 | Catalyst for hydrogenation reaction and preparation method thereof |
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