CN110483242A - A kind of method of 1,4- butynediols hydrogenation synthesis 1,4- butanediol - Google Patents
A kind of method of 1,4- butynediols hydrogenation synthesis 1,4- butanediol Download PDFInfo
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- CN110483242A CN110483242A CN201910859986.0A CN201910859986A CN110483242A CN 110483242 A CN110483242 A CN 110483242A CN 201910859986 A CN201910859986 A CN 201910859986A CN 110483242 A CN110483242 A CN 110483242A
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
Abstract
The invention discloses a kind of methods of 1,4- butynediols hydrogenation synthesis 1,4- butanediol.The following steps are included: Isosorbide-5-Nitrae-butynediols is carried out hydrogenation reaction on modified Ni base catalyst in one-stage hydrogenation reactor, release separation obtains one-stage hydrogenation product；Modified its active component of Ni base catalyst is Ni, at least one of auxiliary agent Ru, K or Mg；Gained one-stage hydrogenation product is carried out secondary hydrogenation with Ru base catalyst to react in second-stage hydrogenation reactor, release separation obtains 1,4-butanediol；Its active component of Ru base catalyst is Ru.The mode that the present invention combines modified Ni base catalyst and Ru base catalyst, makes Isosorbide-5-Nitrae-butynediols conversion ratio reach 100%, the selectivity of 1,4-butanediol reaches 98%, has catalytic activity good, selectivity is high, and reaction condition is mild, by-product species are few, the advantages of being easily isolated.
Description
Technical field
The invention belongs to technical field of fine.More particularly, to a kind of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis Isosorbide-5-Nitrae-
The method of butanediol.
Background technique
1,4-butanediol is a kind of important Organic Chemicals, can be used for producing poly butylene succinate, is poly- to benzene
Dioctyl phthalate butanediol ester, tetrahydrofuran etc. also act as solvent, chain extender and crosslinking agent etc..
Reppe synthetic method is a kind of method of widely used industrialized production 1,4- butanediol.This method with acetylene and
Formaldehyde is raw material, first synthesizes Isosorbide-5-Nitrae-butynediols under copper catalyst effect by acetylene and formaldehyde, Isosorbide-5-Nitrae-butynediols is again through urging
Change plus hydrogen produces 1,4- butanediol.Hydrogenation process generallys use two-step method progress, and one-stage hydrogenation is usually in suspended-bed reactor
Or carried out in fixed bed reactors, using the nickel-base catalyst of Raney's nickel, modified Raney's nickel or precipitation method preparation, two sections add
Hydrogen carries out in fixed bed reactors, mostly uses Raney nickel.The side of 1,4- butanediol is produced so far in industrial application
The shortcomings that method, is the high demand to nickel, and nickel is used as the hydrogenation catalyst of Ruan's inner mold in these methods.Corpuscular nickel is urged
Agent usually uses in a continuous process, is introduced into as disactivation precursor in reactor and is carried out and leaching aluminium
In-situ activation.The bulk density of these catalyst is typically larger than 1.5kg/L, to use catalyst to fill 5~50m3Reactor,
According to the regular activated needs of these catalyst to obtain enough yields in the case where, use 8~100 tons of nickel.And nickel exists
Mass fraction is about 0.01% in the earth's crust, and content is limited, is rarer one of metal.
3449445 A of american documentation literature US reports a kind of side that 1,4- butynediols adds hydrogen to prepare 1,4- butanediol
Method, this method use low-voltage hydrogenation at one section, and two sections use high-pressure hydrogenation, and hydrogenation pressure is greater than 13MPa, and pressure is excessive, energy consumption
Consumption is high.
The Raney nickel that 1242358 A of british patent document GB uses Mo modified realizes Isosorbide-5-Nitrae-butine at high temperature under high pressure
Glycol adds hydrogen 1,4- butanediol.
Based on above-mentioned analysis, low-voltage hydrogenation process would generally generate a large amount of polycondensation aldehyde, while also result in butylene glycol
Isomerization generate a large amount of hydroxybutyraldehyde, increase separation costs, and high-pressure hydrogenation can reduce the production of by-product, still
Need to consume a large amount of energy, while the requirement to equipment is also higher, fixed capital investment increases.
Summary of the invention
Primary and foremost purpose of the invention is to overcome the deficiencies in the prior art described above, and provides a kind of Isosorbide-5-Nitrae-butynediols and hydrogen is added to close
At the method for 1,4- butanediol.This method uses two-stage hydrogenation technique, has catalytic activity good, and selectivity is high, reaction condition temperature
It is few with by-product species, the advantages of being easily isolated, meet the requirement of green chemistry.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of method of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol, comprising the following steps:
S1. 1,4- butynediols is contacted in one-stage hydrogenation reactor with modified Ni base catalyst and carries out one-stage hydrogenation
Reaction, release separation, obtains one-stage hydrogenation product；Wherein, the modified Ni base catalyst is by active component, auxiliary agent and carrier system
It is standby to form, active component Ni, at least one of auxiliary agent Ru, K or Mg；
S2. gained one-stage hydrogenation product in step S2 is contacted and is carried out in second-stage hydrogenation reactor with Ru base catalyst
Secondary hydrogenation reaction, release separation, obtains 1,4-butanediol；Wherein, the Ru base catalyst is by active component, auxiliary agent and carrier
It is prepared, active component Ru, auxiliary agent is K or Mg.
The present invention makes the conversion of Isosorbide-5-Nitrae-butynediols in such a way that modified Ni base catalyst and Ru base catalyst combine
Rate reaches 100%, and the selectivity of 1,4-butanediol reaches 98%, has catalytic activity good, and selectivity is high, reaction condition is mild,
The advantages of by-product species are few, are easily isolated meets the requirement of green chemistry.
Preferably, in modified Ni base catalyst described in S1., in terms of metallic element quality, active component mass percentage
It is 2~50%, auxiliary agent mass percentage is 0.1~5%, and carrier quality percentage composition is 45~97.9%.
It is highly preferred that in terms of metallic element quality, active component quality percentage contains in modified Ni base catalyst described in S1.
Amount is 10~20%, and auxiliary agent mass percentage is 0.5~4%, and carrier quality percentage composition is 76~89.5%.
Preferably, in Ru base catalyst described in S2., in terms of metallic element quality, active component mass percentage is 0.5
~10%, auxiliary agent mass percentage is 0.5~5%, and carrier quality percentage composition is 85~98.5%.
It is highly preferred that in the Ru base catalyst, in terms of metallic element quality, active component mass percentage is 1~
4%, auxiliary agent mass percentage is 1~5%, and carrier quality percentage composition is 91~98%.
Preferably, the carrier in the modified Ni base catalyst and the Ru base catalyst is vermiculite, montmorillonite, bumps
One or more of stick, diatomite, hydrotalcite, aluminum oxide, silica or active carbon.
Preferably, the preparation step of the modified Ni base catalyst and the Ru base catalyst includes: by active component, helps
The soluble-salt of agent is made into mixed solution, is added carrier, and stirring 1~for 24 hours；Then alkaline solution is added and adjusts pH=9~10, holds
Continuous stirring 0.5~for 24 hours, stands overnight, filters, then be washed with deionized, dry, restored after being fired to get.
It is highly preferred that carrier is added, 2~3h is stirred；Then alkaline solution is added, persistently stirs 4~6h.
Preferably, the alkali of the alkaline solution is selected from ammonium hydroxide, urea, potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate
At least one of solution；The concentration of the alkaline solution is 1~2mol/L.
It is highly preferred that the alkali of the alkaline solution is ammonium hydroxide or urea liquid.
Preferably, it is argon gas or air that the condition of the roasting, which includes: calcination atmosphere, and maturing temperature is 200~700 DEG C,
Calcining time is 2~6h.
It is highly preferred that maturing temperature is 500~700 DEG C, calcining time is 4~6h.
Preferably, the condition of the reduction include: reducing agent be hydrogen or be hydrogen and argon gas gaseous mixture, reduction temperature
200~700 DEG C of degree, recovery time are 2~10h.
It is highly preferred that the reduction temperature is 300~600 DEG C, the recovery time is 3~8h.
Preferably, the drying temperature of the modified Ni base catalyst is 60~120 DEG C；The Ru base catalyst is in room temperature 20
It is dry at~30 DEG C.
Preferably, it is 2~8MPa that the condition of one-stage hydrogenation reaction, which includes: Hydrogen Vapor Pressure, 60~130 DEG C of temperature.
It is highly preferred that it is 2.5~4.5MPa, temperature 70~100 that the condition of the one-stage hydrogenation reaction, which includes: Hydrogen Vapor Pressure,
℃。
Preferably, it is 0.5~3MPa that the condition of secondary hydrogenation reaction, which includes: Hydrogen Vapor Pressure, 30~90 DEG C of temperature.
It is highly preferred that it is 1~2MPa that the condition of secondary hydrogenation reaction, which includes: Hydrogen Vapor Pressure, 35~50 DEG C of temperature.
Compared with prior art, the invention has the following advantages:
The mode that the modified Ni base catalyst of the present invention and Ru base catalyst combine, makes two-stage hydrogenation reaction in mild item
It is carried out under part, and higher catalytic activity and lower by-product is kept to be distributed, reduce separation costs, Isosorbide-5-Nitrae-butynediols
Conversion ratio reaches 100%, and the selectivity of 1,4-butanediol reaches 98%, has catalytic activity good, and selectivity is high, reaction condition temperature
It is few with by-product species, the advantages of being easily isolated, meet the requirement of green chemistry.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but embodiment the present invention is not done it is any type of
It limits.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
The preparation of Examples 1 to 8 one-stage hydrogenation catalysts 1~8
The composition of one-stage hydrogenation catalysts 1~8 is as shown in table 1.
Weigh respectively a certain amount of ruthenium trichloride, nickel nitrate, auxiliary agent soluble salt be dissolved in 50mL water, then be added 3g carry
Body continues to stir 6h；It adds 1mol/L ammonium hydroxide and adjusts pH=9~10, persistently stir 4h, stand overnight；It filters, deionized water
Washing, 120 DEG C of dryings restore 3h in 300 DEG C of hydrogen atmospheres of temperature in argon gas after 700 DEG C of roasting 2h, obtain one section and add
Hydrogen catalysts 1~8 (are shown in Table 1).
The preparation of 9~16 secondary hydrogenation catalysts 9~16 of embodiment
The composition of secondary hydrogenation catalysts 9~16 is as shown in table 1.
The soluble salt of a certain amount of ruthenium trichloride, auxiliary agent is dissolved in 30mL deionized water, 5g carrier is then added, is continued
Stir 2h；It adds 1mol/L sodium hydroxide solution and adjusts pH=9~10, persistently stir 4h, stand overnight；It filters, deionization
Water washing is dried under room temperature, in argon gas after 200 DEG C of roasting 6h, is restored 8h in 600 DEG C of hydrogen atmospheres of temperature, is obtained
To secondary hydrogenation catalysts 9~16 (being shown in Table 1).
The method of 17 1,4- butynediols hydrogenation synthesis 1,4- butanediol of embodiment
One-stage hydrogenation step: being added Isosorbide-5-Nitrae-butynediols aqueous solution of 100mL 40% in 250mL autoclave, is added one section
Any one of catalyst for hydrogenation 1~8, sealing, inflated with nitrogen replace 4 times, are filled with Hydrogen Vapor Pressure to 2MPa pressure, are warming up to
It 130 DEG C, continues stirring until reacting kettle inner pressure and is not changing, catalyst is isolated in release, obtains one-stage hydrogenation product.
Secondary hydrogenation step: one-stage hydrogenation product is added in 250mL autoclave, and secondary hydrogenation catalysts 9 are added
Any one of~16, sealing, inflated with nitrogen is replaced 4 times, is filled with Hydrogen Vapor Pressure to 1MPa pressure, is warming up to 90 DEG C, lasting stirring
Do not changing to reacting kettle inner pressure, catalyst is isolated in release, obtains final hydrogenation products 1,4-butanediol.Product after reaction
Distribution is as shown in table 2.
The method of 18 1,4- butynediols hydrogenation synthesis 1,4- butanediol of embodiment
One-stage hydrogenation step: being added Isosorbide-5-Nitrae-butynediols aqueous solution of 100mL 40% in 250mL autoclave, is added one section
Any one of catalyst for hydrogenation 1~8, sealing, inflated with nitrogen replace 4 times, are filled with Hydrogen Vapor Pressure to 8MPa pressure, are warming up to
It 60 DEG C, continues stirring until reacting kettle inner pressure and is not changing, catalyst is isolated in release, obtains one-stage hydrogenation product.
Secondary hydrogenation step: one-stage hydrogenation product is added in 250mL autoclave, and secondary hydrogenation catalysts 9 are added
Any one of~16, sealing, inflated with nitrogen is replaced 4 times, is filled with Hydrogen Vapor Pressure to 3MPa pressure, is warming up to 40 DEG C, lasting stirring
Do not changing to reacting kettle inner pressure, catalyst is isolated in release, obtains final hydrogenation products 1,4-butanediol.Product after reaction
Distribution is as shown in table 3.
The method of 19 1,4- butynediols hydrogenation synthesis 1,4- butanediol of embodiment
One-stage hydrogenation step: being added Isosorbide-5-Nitrae-butynediols aqueous solution of 100mL 40% in 250mL autoclave, is added one section
Any one of catalyst for hydrogenation 1~8, sealing, inflated with nitrogen are replaced 4 times, are filled with Hydrogen Vapor Pressure to 2.5MPa pressure, heating
It to 100 DEG C, continues stirring until reacting kettle inner pressure and is not changing, catalyst is isolated in release, obtains one-stage hydrogenation product.
Secondary hydrogenation step: one-stage hydrogenation product is added in 250mL autoclave, and secondary hydrogenation catalysts 9 are added
Any one of~16, sealing, inflated with nitrogen is replaced 4 times, is filled with Hydrogen Vapor Pressure to 1MPa pressure, is warming up to 50 DEG C, lasting stirring
Do not changing to reacting kettle inner pressure, catalyst is isolated in release, obtains final hydrogenation products 1,4-butanediol.Product after reaction
Distribution is as shown in table 4.
The method of 20 1,4- butynediols hydrogenation synthesis 1,4- butanediol of embodiment
One-stage hydrogenation step: being added Isosorbide-5-Nitrae-butynediols aqueous solution of 100mL 40% in 250mL autoclave, is added one section
Any one of catalyst for hydrogenation 1~8, sealing, inflated with nitrogen are replaced 4 times, are filled with Hydrogen Vapor Pressure to 4.5MPa pressure, heating
It to 70 DEG C, continues stirring until reacting kettle inner pressure and is not changing, catalyst is isolated in release, obtains one-stage hydrogenation product.
Secondary hydrogenation step: one-stage hydrogenation product is added in 250mL autoclave, and secondary hydrogenation catalysts 9 are added
Any one of~16, sealing, inflated with nitrogen is replaced 4 times, is filled with Hydrogen Vapor Pressure to 2MPa pressure, is warming up to 35 DEG C, lasting stirring
Do not changing to reacting kettle inner pressure, catalyst is isolated in release, obtains final hydrogenation products 1,4-butanediol.Product after reaction
Distribution is as shown in table 5.
The composition of table 1 one-stage hydrogenation catalysts 1~8 and secondary hydrogenation catalysts 9~16
2 embodiment of table, 17 result
3 embodiment of table, 18 result
4 embodiment of table, 19 result
5 embodiment of table, 20 result
As can be seen from the above embodiments, the mode that the modified Ni base catalyst of the present invention and Ru base catalyst combine, makes
Two-stage hydrogenation reaction carries out in a mild condition, and higher catalytic activity and lower by-product is kept to be distributed, and reduces
Separation costs, Isosorbide-5-Nitrae-butynediols conversion ratio can reach 100%, and the selectivity of 1,4-butanediol reaches 98%, have catalysis
Activity is good, and selectivity is high, and reaction condition is mild, by-product species are few, the advantages of being easily isolated, meets wanting for green chemistry
It asks.
In addition by table 2 to table 5 it is found that under equal conditions, Isosorbide-5-Nitrae-butynediols conversion ratio of embodiment 19 and embodiment 20
It is slightly good with the productivity ratio embodiment 17 and embodiment 18 of 1,4-butanediol, illustrate when one-stage hydrogenation react: Hydrogen Vapor Pressure be 2.5~
4.5MPa, 70~100 DEG C of temperature；Secondary hydrogenation reaction: Hydrogen Vapor Pressure is 1~2MPa, at 35~50 DEG C of temperature, Isosorbide-5-Nitrae-butine two
The yield of alcohol conversion and 1,4- butanediol is higher.
The preferred embodiment that the above specific embodiment is of the invention for ease of understanding and illustrates, but the invention is not limited to
Above-described embodiment does not mean that the present invention must rely on above-described embodiment and could implement.Person of ordinary skill in the field
It is the addition of equivalence replacement and auxiliary element to raw material selected by the present invention, specific it will be clearly understood that any improvement in the present invention
The selection etc. of mode, all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of Isosorbide-5-Nitrae-butynediols hydrogenation synthesis 1,4-butanediol method, which comprises the following steps:
S1. 1,4- butynediols is contacted in one-stage hydrogenation reactor with modified Ni base catalyst and to carry out one-stage hydrogenation anti-
It answers, release separation obtains one-stage hydrogenation product；Wherein, the modified Ni base catalyst is prepared by active component, auxiliary agent and carrier
It forms, active component Ni, at least one of auxiliary agent Ru, K or Mg；
S2. gained one-stage hydrogenation product in step S2 is contacted in second-stage hydrogenation reactor with Ru base catalyst and carries out two sections
Hydrogenation reaction, release separation, obtains 1,4-butanediol；Wherein, the Ru base catalyst is prepared by active component, auxiliary agent and carrier
It forms, active component Ru, auxiliary agent is K or Mg.
2. the method according to claim 1, wherein being modified in Ni base catalyst described in S1., with metallic element matter
Meter, active component mass percentage are 2~50%, and auxiliary agent mass percentage is 0.1~5%, and carrier quality percentage contains
Amount is 45~97.9%.
3. according to the method described in claim 2, it is characterized in that, being modified in Ni base catalyst described in S1., with metallic element matter
Meter, active component mass percentage are 10~20%, and auxiliary agent mass percentage is 0.5~4%, and carrier quality percentage contains
Amount is 76~89.5%.
4. the method according to claim 1, wherein in Ru base catalyst described in S2., with metallic element quality
Meter, active component mass percentage are 0.5~10%, and auxiliary agent mass percentage is 0.5~5%, and carrier quality percentage contains
Amount is 85~98.5%.
5. according to the method described in claim 4, it is characterized in that, in Ru base catalyst described in S2., with metallic element quality
Meter, active component mass percentage are 1~4%, and auxiliary agent mass percentage is 1~5%, and carrier quality percentage composition is 91
~98%.
6. the method according to claim 1, wherein in the modified Ni base catalyst and the Ru base catalyst
Carrier be one of vermiculite, montmorillonite, concave convex rod, diatomite, hydrotalcite, aluminum oxide, silica or active carbon
Or it is several.
7. the method according to claim 1, which is characterized in that the modified Ni base catalyst and the Ru base
The preparation step of catalyst includes:
The soluble-salt of the active component, auxiliary agent is made into mixed solution, is added carrier, stirring 1~for 24 hours；Then alkali is added
Property solution adjust pH=9~10, persistently stir 0.5~for 24 hours, stand overnight, filter, then be washed with deionized, it is dry, through roasting
After burning restore to get.
8. the method according to the description of claim 7 is characterized in that the alkali of the alkaline solution is selected from ammonium hydroxide, urea, hydroxide
At least one of potassium, sodium hydroxide, potassium carbonate or sodium carbonate liquor；The concentration of the alkaline solution is 1~2mol/L.
9. the method according to the description of claim 7 is characterized in that the condition of the roasting include: calcination atmosphere be argon gas or
Air, maturing temperature are 200~700 DEG C, and calcining time is 2~6h；The condition of the reduction include: reducing agent be hydrogen or
For the gaseous mixture of hydrogen and argon gas, 200~700 DEG C of reduction temperature, the recovery time is 2~10h.
10. the method according to claim 1, wherein the condition of one-stage hydrogenation reaction includes: Hydrogen Vapor Pressure
For 2~8MPa, 60~130 DEG C of temperature；It is 0.5~3MPa, temperature 30 that the condition of the secondary hydrogenation reaction, which includes: Hydrogen Vapor Pressure,
~90 DEG C.
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| CN102408307A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing butanediol by carrying out two-stage catalytic hydrogenation on butynediol |
| CN107778137A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | The method for preparing 1,4 butanediols |
| CN107778138A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method that Isosorbide-5-Nitrae butynediols two-stage hydrogenation prepares Isosorbide-5-Nitrae butanediol |
| CN108993592A (en) * | 2018-06-13 | 2018-12-14 | 厦门大学 | A kind of efficient hydrogenation catalyst and the preparation method and application thereof of butynediols butanediol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112473679A (en) * | 2020-11-30 | 2021-03-12 | 山西大学 | Nickel-phyllosilicate structure catalyst and preparation method thereof |
| CN112473679B (en) * | 2020-11-30 | 2021-12-31 | 山西大学 | Nickel-phyllosilicate structure catalyst and preparation method thereof |
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