CN105646142B - A kind of method for being catalyzed ester through hydrogenation alcohol - Google Patents
A kind of method for being catalyzed ester through hydrogenation alcohol Download PDFInfo
- Publication number
- CN105646142B CN105646142B CN201410720107.3A CN201410720107A CN105646142B CN 105646142 B CN105646142 B CN 105646142B CN 201410720107 A CN201410720107 A CN 201410720107A CN 105646142 B CN105646142 B CN 105646142B
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- catalyst
- reaction
- ester
- organic 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method for being catalyzed ester through hydrogenation alcohol, the hydrogenation catalyst that metal organic acid salt and alkyl aluminum act on obtaining is used for the hydrogenation reaction of ester type compound by this method, prepares alcohol compound.The advantages of this method is：The preparation process of catalyst is simple, and dosage is few, than traditional ester through hydrogenation catalyst it is active it is high, selectivity is good, avoid using noble ruthenium and poisonous chromium that reaction condition is more gentle, small to equipment corrosion as catalyst.
Description
Technical field
The present invention relates to a kind of method for being catalyzed ester through hydrogenation alcohol, specifically metal organic acid salt and alkyl aluminum are made
It is used for the hydrogenation reaction of ester type compound with obtained hydrogenation catalyst, prepares corresponding alcohol compound.
Background technology
The alcohol compound such as conduct such as ethanol, ethylene glycol, 1,3-PD, terephthalyl alcohol and Isosorbide-5-Nitrae-cyclohexane dimethanol
The organic synthesis intermediate of high added value, tool have been widely used, and market demand is larger.Usual alcohol compound can pass through
Corresponding sour direct hydrogenation is made, but strong to equipment corrosion, and process conditions are harsher.And ester type compound wide material sources,
Mature production technology, but downstream demand is limited.Therefore, using ester type compound as raw material, by the method for catalytic hydrogenation, phase is prepared
The alcohol compound answered, the technique have potential economic benefit and actual application value.
At present, the reaction of ester type compound preparing alcohol by hydrogenating relative, the catalyst of use are broadly divided into two classes.It is wherein homogeneous
Ruthenium catalyst is one of object of people's research.Elsevier et al. uses CH3C(CH2PPh2)3As Ru (acac)3Part
To be catalyzed preparation of ethanediol by dimethyl oxalate hydrogenation, dimethyl oxalate conversion ratio is 100%, glycol selectivity 95%
(J.Mol.Catal.A:Chem.2003,206,185-192).Ruthenium catalyst there is price it is high, prepare and the life-span is shorter etc.
Problem, limit its commercial Application.Another kind of widely used ester through hydrogenation catalyst is mainly copper-based catalysts, can be selective
Ground hydrogenates C-O keys, and retains C-C keys.Copper-based catalysts are primarily present that the life-span is undesirable, anti-caking power is poor, mechanical strong
Spend the problems such as relatively low.Therefore researcher improves the performance of copper-based catalysts by introducing other suitable auxiliary agents.Davis et al.
Using the hydrogenation reaction of copper chromium catalysis ethyl acetate, ethyl acetate conversion ratio is 90%, ethanol selectivity 93%
(Top.Catal.2014,57,757-761).But chromium is known from experience to people produces strong toxic action, seriously pollutes environment, thus
Industrially strictly prohibit the use of chromium-containing catalyst in recent years.In addition copper-based catalysts common problem is that reaction needs are higher
180-280 DEG C of temperature, energy consumption is big；The interior diffusion of ester compounds molecule in the catalyst causes hydrogenation reaction speed slower,
Higher hydrogen ester ratio is needed, and reduces the problem of catalyst particle size can cause bed resistance to increase.Therefore, a kind of condition is developed
The method of the efficient catalytic ester through hydrogenation of milder is significant.
The content of the invention：
It is an object of the invention to provide a kind of method for being catalyzed ester through hydrogenation alcohol, this method is by metal organic acid salt and alkane
The hydrogenation catalyst that base aluminium acts on obtaining is used for the hydrogenation reaction of ester type compound, prepares corresponding alcohol compound.
Metal organic acid salt used is one kind in nickel iso-caprylate, nickel naphthenate, isooctyl acid copper, cobalt iso-octoate in this method
It is or a variety of.Alkyl aluminum is the one or more in triethyl aluminum, three second butyl aluminium, trioctylaluminum, tri-n-hexyl aluminum.Metal
The molar ratio of acylate (being counted using metal) and alkyl aluminum (being counted using aluminium) is 0.01-1, and the metal organic acid salt of optimization is (with gold
Category meter) and alkyl aluminum molar ratio (is counted) using aluminium as 0.05-0.5.
Hydrogenation catalyst typical production in this method is：At nitrogen protection, 20-70 DEG C, according to the above ratio will
Alkyl aluminum is slowly dropped to (in terms of aluminium atom) in metal organic acid salt (in terms of metal), continues to stir 0.1- after being added dropwise
2.0h。
Ester type compound used is the one or more in having structure in the present invention：
The mol ratio of used catalyst (being counted using metal) and ester type compound is 10 in this method-5-10-3。
Ester through hydrogenation reaction is carried out in pressure reactor.Wherein hydrogen partial pressure is 0.01-5.0MPa, and optimal hydrogen partial pressure is
1.5-3.0MPa.Reaction temperature is 100 DEG C -200 DEG C, and the optimal reaction temperature of optimization is 140-180 DEG C.Reaction time is 0.5-
5h, the optimum reacting time of optimization is 2-4h.
Compared with prior art, the invention has the advantages that：
(1) this method can realize that ester through hydrogenation prepares alcohol under conditions of more gently.The activity of catalyst is high, target production
The selectivity of thing is more preferable.
(2) catalyst preparation process is simple, dosage is few, cost is cheap, small toxicity, has potential application prospect.
Brief description of the drawings
Fig. 1 is that nickel iso-caprylate is catalyzed the dimethyl oxalate conversion ratio of Hydrogenation of Dimethyl Oxalate reaction with temperature with triethyl aluminum
Variation diagram；
Fig. 2 is that nickel iso-caprylate and the glycol selectivity of triethyl aluminum catalysis Hydrogenation of Dimethyl Oxalate reaction vary with temperature
Figure；
Fig. 3 is that nickel iso-caprylate is catalyzed the dimethyl oxalate conversion ratio of Hydrogenation of Dimethyl Oxalate reaction with the time with triethyl aluminum
Variation diagram；
Fig. 4 is that nickel iso-caprylate and the glycol selectivity of triethyl aluminum catalysis Hydrogenation of Dimethyl Oxalate reaction change over time
Figure；
Fig. 5 is that the nickel iso-caprylate of different mol ratio example is catalyzed the oxalic acid diformazan of Hydrogenation of Dimethyl Oxalate reaction with triethyl aluminum
Ester conversion rate figure；
Fig. 6 is the ethylene glycol choosing that the nickel iso-caprylate of different mol ratio example and triethyl aluminum are catalyzed Hydrogenation of Dimethyl Oxalate reaction
Selecting property figure；
The present invention is described in detail with embodiment below.
Specific embodiment：
Embodiment 1-8：Under different temperatures, the catalyst Hydrogenation of Dimethyl Oxalate of nickel iso-caprylate and triethyl aluminum composition
Prepare the reaction result of ethylene glycol as shown in Figure 1-2.Specific experiment process description is as follows：
At nitrogen protection, 50 DEG C, 11.2g triethyl aluminums are slowly dropped in 3.45g nickel iso-caprylates, and continue to stir
1.0h, the hydrogenation catalyst of high activity is made.
By 11.8g dimethyl oxalates, 0.01g catalyst obtained above, 50mL hexamethylenes are added in 100mL reactors,
Hydrogen is filled with to 2MPa, is stirred continuously down, keeps 4.5h at different temperatures.If hydrogen partial pressure declines, hydrogen make-up is extremely
2MPa.After reaction terminates, room temperature is cooled to.Product analysis uses gas chromatography.Reaction extracts reaction solution direct progress after terminating
Gas chromatographic analysis.
It is from the figure, it can be seen that anti-using nickel iso-caprylate and catalyst Hydrogenation of Dimethyl Oxalate that triethyl aluminum forms
At once, dimethyl oxalate conversion ratio is all raised with reaction temperature and improved constantly, and the selectivity of ethylene glycol is more than in reaction temperature
Start to reduce at 160 DEG C.Temperature is too high, and side reaction increases so that ethylene glycol yield reduces.Therefore, optimal reaction temperature is set as
140-180℃。
Embodiment 9-16：Differential responses time, the catalyst dimethyl oxalate of nickel iso-caprylate and triethyl aluminum composition
Hydrogenation for ethylene glycol reaction result as shown in Figure 3-4.Specific experiment process description is as follows：
By 11.8g dimethyl oxalates, 0.01g catalyst obtained above, 50mL hexamethylenes are added in 100mL reactors,
Hydrogen is filled with to 2MPa, is stirred continuously down and is warming up to 170 DEG C, and keep the differential responses time respectively.If hydrogen partial pressure declines,
Hydrogen make-up is to 2MPa.After reaction terminates, room temperature is cooled to.Product analysis uses gas chromatography.Reaction negates after terminating should
Liquid directly carries out gas chromatographic analysis.
It is from the figure, it can be seen that anti-using nickel iso-caprylate and catalyst Hydrogenation of Dimethyl Oxalate that triethyl aluminum forms
At once, dimethyl oxalate conversion ratio with the reaction time extend improve constantly, and the selectivity of ethylene glycol in the reaction time more than 3h
After start to reduce.Overlong time, side reaction increases so that ethylene glycol yield reduces.Therefore, optimal reaction temperature is set as 2-4h.
Embodiment 17-22：The catalyst dimethyl oxalate that the nickel iso-caprylate of different proportion forms with triethyl aluminum adds
Hydrogen prepares the reaction result of ethylene glycol as seen in figs. 5-6.Specific experiment process description is as follows：
At nitrogen protection, 50 DEG C, 11.42g, the second of 5.71g, 2.28g, 1.14g, 0.23g and 0.11g tri- will be contained respectively
Base aluminum solutions are slowly dropped to containing in 0.35g nickel iso-caprylate solution, and continue to stir 1.0h, and the hydrogenation catalyst of high activity is made
Agent.
By 11.8g dimethyl oxalates, 10-5Mol catalyst obtained above (in terms of nickel), 50mL hexamethylenes add 100mL
In reactor, hydrogen is filled with to 2MPa, is stirred continuously down and is warming up to 170 DEG C, and keep 4h.If hydrogen partial pressure declines, supplement
Hydrogen is to 2MPa.After reaction terminates, room temperature is cooled to.Product analysis uses gas chromatography.Reaction extracts reaction solution straight after terminating
Tap into promoting the circulation of qi analysis of hplc.
From the figure, it can be seen that with the raising of nickel iso-caprylate (in terms of nickel)/triethyl aluminum (in terms of aluminium) molar ratio, oxalic acid
The conversion ratio of dimethyl ester and the selectivity of ethylene glycol gradually reduce.When triethyl aluminum ratio is too low, it can not be with nickel iso-caprylate
Effect completely, influences catalytic activity.When nickel iso-caprylate ratio is too high, excessive nickel ion causes the generation of side reaction.
Embodiment 23-28：The reaction result of various ester type compound catalytic hydrogenations is as shown in table 1.Specific experiment process is retouched
State as follows：
By 0.1mol ester type compounds (ethyl acetate, diethy-aceto oxalate, dimethyl malenate, dimethyl terephthalate (DMT),
Isosorbide-5-Nitrae-cyclohexyldicarboxylic acids dimethyl ester), (both molar ratios are 0.1) that 0.01g nickel iso-caprylate and triethyl aluminum form is urged
Agent, 50mL hexamethylenes add in 100mL reactors, are filled with hydrogen to 2MPa, are stirred continuously down and are warming up to 170 DEG C, and keep
4h.If hydrogen partial pressure declines, hydrogen make-up 2MPa.After reaction terminates, room temperature is cooled to.Product analysis uses gas-chromatography
Method.Reaction directly extracts reaction solution carry out gas chromatographic analysis after terminating.
As can be seen from the table, all kinds of ester type compounds can realize efficient catalytic hydrogenation under the catalyst system and catalyzing.
Table 1
It is described above, some embodiments only of the present invention, but protection scope of the present invention is not limited to that,
Not because each embodiment precedence to the present invention caused by any restrictions, it is any to be familiar with person skilled in the art of the present invention and exist
In the technical scope that the present invention reports, it can be changed or replace easily, should all be included within the scope of the present invention.Cause
This, protection scope of the present invention is not limited only to above example, it should is defined by scope of the claims.
Claims (5)
- A kind of 1. method for being catalyzed ester through hydrogenation alcohol, it is characterised in that：Add what metal organic acid salt and alkyl aluminum acted on obtaining Hydrogen catalyst is used in the hydrogenation reaction of ester type compound, prepares alcohol compound；The metal organic acid salt be nickel iso-caprylate, nickel naphthenate, isooctyl acid copper, one kind in cobalt iso-octoate or two kinds with On；Ester type compound is one kind or more than two kinds in having structure：The hydrogen partial pressure for being catalyzed ester through hydrogenation reaction is 1.5-3.0MPa；Reaction temperature is 140-180 DEG C；Reaction time is 2-5h.
- 2. in accordance with the method for claim 1, it is characterised in that：The alkyl aluminum is triethyl aluminum, three second butyl aluminium, three pungent One kind in base aluminium, tri-n-hexyl aluminum or more than two kinds.
- 3. according to the method described in claim 1 or 2, it is characterised in that：The preparation process of the hydrogenation catalyst is：In nitrogen Protect, at 20-70 DEG C, alkyl aluminum is slowly dropped in metal organic acid salt, continue to stir 0.1-2.0h after being added dropwise.
- 4. in accordance with the method for claim 3, it is characterised in that：The mol ratio of the metal organic acid salt and alkyl aluminum is 0.01-1。
- 5. according to the method described in claim 1 or 5, it is characterised in that：Used catalyst is with metal in catalysis ester through hydrogenation reaction The mol ratio of acylate meter and ester type compound is 10-5-10-3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410720107.3A CN105646142B (en) | 2014-12-02 | 2014-12-02 | A kind of method for being catalyzed ester through hydrogenation alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410720107.3A CN105646142B (en) | 2014-12-02 | 2014-12-02 | A kind of method for being catalyzed ester through hydrogenation alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105646142A CN105646142A (en) | 2016-06-08 |
| CN105646142B true CN105646142B (en) | 2017-12-26 |
Family
ID=56481137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410720107.3A Active CN105646142B (en) | 2014-12-02 | 2014-12-02 | A kind of method for being catalyzed ester through hydrogenation alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105646142B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037729A (en) * | 1988-05-21 | 1989-12-06 | 中国石油化工总公司辽阳石油化纤公司 | A kind of benzene hydrogenating homogeneous catalyst |
| CN1162951A (en) * | 1994-11-07 | 1997-10-22 | 国际壳牌研究有限公司 | Process and catalyst for the direct hydrogenation of carboxylic esters |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003096422A (en) * | 2001-09-26 | 2003-04-03 | Kuraray Co Ltd | Adhesive composition and adhesive article |
-
2014
- 2014-12-02 CN CN201410720107.3A patent/CN105646142B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037729A (en) * | 1988-05-21 | 1989-12-06 | 中国石油化工总公司辽阳石油化纤公司 | A kind of benzene hydrogenating homogeneous catalyst |
| CN1162951A (en) * | 1994-11-07 | 1997-10-22 | 国际壳牌研究有限公司 | Process and catalyst for the direct hydrogenation of carboxylic esters |
Non-Patent Citations (1)
| Title |
|---|
| 齐格勒-纳塔均相加氢催化剂的制备、性能与应用;唐占忠;《工业催化》;19951231(第1期);第11-13页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105646142A (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102807483B (en) | Method for preparing cyclopentanone and/or cyclopentanol by furfural or furfuryl alcohol | |
| CN103159606B (en) | A kind of take furfural as the method that cyclopentanone prepared by raw material | |
| CN102688768B (en) | Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof | |
| CN102600842A (en) | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof | |
| CN103087748A (en) | Preparation method of aviation kerosene or diesel | |
| US9434665B2 (en) | Ruthenium complex and method for preparing methanol and diol | |
| CN104711021A (en) | Method for preparing cycloparaffin as aviation kerosene or diesel oil by biomass route | |
| CN103450940A (en) | Method for preparation of aviation kerosene and diesel oil from biomass derivative | |
| CN101475472A (en) | Method for preparing oxalate by coupling reaction of CO in gaseous phase | |
| CN104710282B (en) | Method for producing ethanol co-production methanol | |
| CN102211978B (en) | Method for synthesizing glycol by hydrogenation of dimethyl oxalate | |
| CN103664587B (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN104193606A (en) | Technique for preparing acetone from synthetic gas | |
| CN106365994B (en) | A kind of production method of lower aliphatic carboxylic acid's Arrcostab | |
| CN102649081A (en) | Reducing method for preparation of ethylene glycol catalyst by oxalate through hydrogenation | |
| CN104447164B (en) | A kind of method preparing propylene from oxidative dehydrogenation of propane | |
| CN104557454B (en) | A kind of method of acetic acid Hydrogenation for high-quality ethanol | |
| CN105646142B (en) | A kind of method for being catalyzed ester through hydrogenation alcohol | |
| CN101993347A (en) | Method for producing ethanediol from oxalate by hydrogenation | |
| CN110964563B (en) | Hydrofining method for preparing mixed alcohol crude product from synthesis gas | |
| CN108689814A (en) | A kind of technique of synthesis menthones | |
| CN113559935B (en) | Catalyst system and method for preparing hydroxycitronellal from citronellal epoxide | |
| CN109456157A (en) | A method of L- menthones is prepared by R- citronellal | |
| CN104470887B (en) | Prepared the transition metal carbene complexes catalysis process of carboxylate by alcohol under dehydration | |
| CN107793294A (en) | A kind of absolute ethyl alcohol, low-grade ethanol process for refining and purifying |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |