CN109369329A - A kind of method that isoamyl olefine aldehydr selective hydration prepares prenol - Google Patents
A kind of method that isoamyl olefine aldehydr selective hydration prepares prenol Download PDFInfo
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- CN109369329A CN109369329A CN201811604325.5A CN201811604325A CN109369329A CN 109369329 A CN109369329 A CN 109369329A CN 201811604325 A CN201811604325 A CN 201811604325A CN 109369329 A CN109369329 A CN 109369329A
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- prenol
- olefine aldehydr
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- isoamyl olefine
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a kind of method that isoamyl olefine aldehydr selective hydration prepares prenol, the methods are as follows: 50~80 DEG C of temperature, 0.1~3.0MPa of pressure, mass space velocity 5~8 hours‑1, hydrogen and isoamyl olefine aldehydr feed material the ratio between amount 1:1~20:1 under conditions of, isoamyl olefine aldehydr and hydrogen are mixed, it is contacted with the Al-Zn/CeO2 catalyst of support type and carries out hydrogenation reaction, obtain prenol, prenol is obtained, catalyst price is lower, selects activity high, prenol can be obtained under conditions of low-temp low-pressure high-speed, reduce prenol and obtain production cost.
Description
Technical field
The present invention relates to the sides that organic chemical industry field more particularly to a kind of isoamyl olefine aldehydr selective hydration prepare prenol
Method.
Background technique
Prenol (3- methyl-2 butenol) is a kind of important medicine, fragrance and pesticide intermediate, can be used for giving birth to
Produce citral, different vegetable alcohol, DV chrysanthemumic acid methyl esters, vitamin E, vitamin A, carotenoid intermediate etc., it can also be used to which other have
Machine synthesis.
At present prenol synthetic method mainly include the following types:
1, isobutene method: patent US4028424 is described using isobutene and formaldehyde as raw material and is made different through prins reaction
Pentenol, but the reaction selectivity is poor, and the selectivity of prenol is about 5%, while generating 80~90% 3- methyl -3-
Butenol；
Patent WO2008037693 is described using isobutene and formaldehyde as raw material and 3- methyl -3- butylene is made through condensation reaction
Alcohol, then isomerization generates 3- methyl-2 butenol, the catalysis on heterogeneous noble metal catalyst by 3- methyl -3- butenol
Agent is made of Pd, Se and Te, and in addition the reaction has 2.5% excessive hydrogenation product isoamyl alcohol to generate；
Patent US4219683 describes that isomery is converted into the presence of palladium catalyst and hydrogen by 3- methyl -3- butenol
Prenol, conversion ratio are 39~54%, selectivity 82~99%.The shortcomings that process route is that isobutene is reacted with formaldehyde
High temperature and pressure is needed, severe reaction conditions, in addition, the isomerization reaction conversion ratio of 3- methyl -3- butenol is low, separating difficulty is big.
2, methyl butenol isomerate process: under alkaline condition, acetone and acetylene ethynylation generate methyl butynol, then
Methyl butenol is obtained with lindlar catalyst plus hydrogen, obtains prenol in isomerization.
It is described in patent US3925485 example with 2- methyl -3- butene-2 alcohol (methyl butenol) for raw material, with positive vanadium
Sour tetrahydro virtue camphor tree ester is catalyst, and 150 DEG C of reaction 7h obtain the conversion ratio 25.6% of prenol, and yield can be to 83%；Patent
CN101381283A, which is described, carries out methyl butenol using one or more of rhenium catalyst, tungsten catalyst and vanadium catalyst
Isomerization reaction can continuously obtain prenol under 130~150 DEG C of temperature, 0.2~0.3MPa of pressure, yield is 86~
93%.The shortcomings that above-mentioned two patents technique is that isomerization reaction is balanced reaction, and conversion ratio is low, and separating difficulty is big, and what is used urges
Agent preparation is difficult, and price is higher.
3, isoamyl olefine aldehydr hydrogenation method: isoamyl olefine aldehydr is subjected to selective hydrogenation, prenol is made.Tomoo et al. (JOrg
Chem 1998,63:2378-2381) to α, beta-unsaturated carbonyl compound has the Rh6 (CO) 16 of high catalytic activity for use
It is catalyst with amine substance, using formic acid and isopropanol as hydrogen source, hydrogenation reaction is carried out to isoamyl olefine aldehydr, conversion ratio is reachable
92%, prenol selectivity 96%, isoamyl alcohol is selective up to 4%.Patent US4929776 uses RuH2 (PPh3) for catalysis
Agent, isopropyl alcohol and water or toluene make solvent, and isoamyl olefine aldehydr is at 35~50 DEG C, and under 2~3MPa plus hydrogen, conversion ratio are different up to 100%
Pentenol is selective up to 90%.
Patent CN1258506C and CN1323059C, which are described, adulterates Al loaded catalyst and Pt/ZnO progress using Ru
The method that olefinic beta-unsaturated carbonyl compounds selective hydrogenation prepares corresponding unsaturated alcohol, wherein the selectivity of unsaturated alcohol reaches
90% or more, saturated alcohols selectivity 4~6%, but the example that isoamyl olefine aldehydr adds hydrogen is not described.
Isoamyl olefine aldehydr adds hydrogen to prepare prenol its technological difficulties and is in isoamyl olefine aldehydr molecule while having C=C and C=
O key, due to C=O bond energy be greater than C=C bond energy, and the two have conjugation so that reaction will on C=O key plus hydrogen and
It is more difficult that C=C key is not destroyed, and isoamyl alcohol (saturated alcohols) product inevitably occurs in hydrogenation process.
Summary of the invention
It is an object of the present invention to provide a kind of methods that isoamyl olefine aldehydr selective hydration prepares prenol, i.e., with support type
The method that Al-Zn/CeO2 catalyst isoamyl olefine aldehydr selective hydration prepares prenol, solves load type palladium or platinum catalyst
The problems such as expensive caused prenol reaction temperature and pressure are high, air speed is low.
The present invention, which provides, a kind of prepares iso-amylene with the Al-Zn/CeO2 catalyst isoamyl olefine aldehydr selective hydration of support type
The method of alcohol, the method are as follows: in 50~80 DEG C of temperature, 0.1~3.0MPa of pressure, mass space velocity 5~8 hours-1, hydrogen with
Under conditions of the ratio between the amount of isoamyl olefine aldehydr feed material 1:1~20:1, isoamyl olefine aldehydr and hydrogen are mixed, the Al- with support type
The contact of Zn/CeO2 catalyst carries out hydrogenation reaction, obtains prenol；It regenerates, recycles after catalyst inactivation；
The Al-Zn/CeO2 catalyst of the support type uses base metal Al and Zn as active component, can be effectively
Improvement isoamyl olefine aldehydr selective hydration prepares isoamyl olefine aldehydr conversion ratio, prenol selectivity and receipts in prenol reaction
Rate.
Under preferable case, the weight ratio of Al and Zn are 1:0.1-10；Preferably, the weight ratio of Al and Zn is 1:0.3-8.It adjusts
The weight ratio of control Al and Zn can preferably improve the conversion ratio of isoamyl olefine aldehydr and selectivity, the yield of prenol.
It prepares isoamyl olefine aldehydr selective hydration provided by the invention the present invention also provides a kind of and prepares urging for prenol
The method of agent, this method comprises: (1) introduces compound containing Al and compound containing Zn in support C eO2, before obtaining catalyst
Body；(2) catalyst precarsor is restored under hydrogen atmosphere, obtains isoamyl olefine aldehydr selective hydration and prepares prenol
Catalyst.
What is provided in method provided by the invention introduces compound containing Al and compound containing Zn in support C eO2, it is therefore an objective to
Active component is finally introduced in the catalyst of prenol in order to prepare to the isoamyl olefine aldehydr selective hydration of preparation, specially
Al3+And Zn2+, Al3+And Zn2+It can be complexed with the carbonyl of isoamyl olefine aldehydr in catalytic reaction process, aldehyde carbonyl groups be activated, so that hydrogen
Occur in aldehyde carbonyl groups with changing reaction selectivity, and then improves the selectivity of prenol, while active component A l3+And Zn2+It is right
The catalytic activity of C=C key is very low, thus avoids the generation of the by-product of over-hydrogenation simultaneously.
Preferably, on the basis of the total weight of catalyst, the content of Al is that the content of 1-25 weight %, Zn are 5-25 weight
The content for measuring % and carrier is 50-94 weight %；It is highly preferred that the content that the content of Al is 7-23 weight %, Zn is 5-20
The content of weight % and carrier is 57-88 weight %.
Preferably, the compound containing Al is at least one of aluminum nitrate, aluminium chloride, protochloride aluminium, nitric acid Asia aluminium.
Preferably, the compound containing Zn can obtain catalyst precarsor and in step (2) for carrier can be added
The substance of Zn can be changed under conditions of reduction.Under preferable case, the compound containing Zn is zinc chloride.
The regeneration method of the Al-Zn/CeO2 catalyst of the support type is off into isoamyl olefine aldehydr raw material, is passed through oxygen
Gas is 100~1000h in 300 DEG C~600 DEG C of temperature, 0.8~6.0MPa of pressure, oxygen volume space velocity-1Under the conditions of inactivation is urged
Agent progress coke-burning regeneration 3~for 24 hours.
Compared with prior art, the present invention has the advantage that
(1) the Al-Zn/CeO2 catalyst price of support type relatively to the selective hydrogenation of aldehyde carbonyl groups in isoamyl olefine aldehydr have compared with
High catalytic activity, at the same it is very low to the catalytic activity of C=C double bond, it can be obtained under conditions of low-temp low-pressure high-speed different
Pentenol reduces prenol and obtains production cost；
(2) catalyst activity stability is good, and the device stable operation time is long, can avoid reactor reaction and regeneration is frequently cut
Change operation；Catalyst is renewable, can avoid a large amount of dead catalyst post-processings, and effect on environment is small.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
[embodiment 1]
A certain amount of aluminum nitrate and four zinc chloride and deionized water are mixed evenly, it is molten to obtain the dipping containing Al-Zn
Liquid；A certain amount of α-CeO2 carrier is added in above-mentioned dipping solution, stands aging for 24 hours at room temperature, then through 80 DEG C of dry 4h,
Catalyst I is made in 700 DEG C of roasting 4h；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere
Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtain catalyst I.By adjusting active component and carrier
Dosage so that the composition of catalyst I are as follows: the content of 9.3 weight %, the α-CeO2 of content of content 11.5 the weight %, Zn of Al
79.2 weight %.
[embodiment 2]
A certain amount of aluminum nitrate and four zinc chloride and deionized water are mixed evenly, it is molten to obtain the dipping containing Al-Zn
Liquid；A certain amount of γ-CeO2 carrier is added in above-mentioned dipping solution, stands aging for 24 hours at room temperature, then through 80 DEG C of dry 4h,
Catalyst precarsor is made in 700 DEG C of roasting 4h；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere
Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtain catalyst II.By adjusting active component and carrier
Dosage so that the composition of catalyst II are as follows: 8.8 weight %, the γ-CeO2's of content of content 13.2 the weight %, Zn of Al contains
Measure 78 weight %.
[embodiment 3]
A certain amount of aluminum nitrate and four zinc chloride and deionized water are mixed evenly, it is molten to obtain the dipping containing Al-Zn
Liquid；A certain amount of γ-CeO2 carrier is added in above-mentioned dipping solution, stands aging for 24 hours at room temperature, then through 80 DEG C of dry 4h,
Catalyst precarsor is made in 700 DEG C of roasting 4h；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 10h, and hydrogen contains in hydrogen atmosphere
Amount is 15 volume %, and the volume space velocity of hydrogen atmosphere is 2000h-1, obtain catalyst III.By adjusting active component and load
The dosage of body, so that the composition of catalyst III are as follows: 12.1 weight %, the γ-CeO2's of content of content 8.6 the weight %, Zn of Al
79.3 weight % of content.
[embodiment 4]
Using fixed-bed reactor, in 220 DEG C of temperature, pressure 0.5MPa, isoamyl olefine aldehydr mass space velocity 11h-1, hydrogen with
Under the reaction condition of second raw materials components mole ratio 10:1, iso-amylene aldehyde hydrogenation reaction is carried out with catalyst I~IV of above-mentioned preparation, is evaluated
The catalytic performance of catalyst, experimental result are listed in table 1.
Table 1
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (6)
1. a kind of method that isoamyl olefine aldehydr selective hydration prepares prenol, it is characterised in that: in 50~80 DEG C of temperature, pressure
0.1~3.0MPa, mass space velocity 5~8 hours-1, hydrogen and isoamyl olefine aldehydr feed material the ratio between amount 1:1~20:1 condition
Under, isoamyl olefine aldehydr and hydrogen are mixed, is contacted with the Al-Zn/CeO2 catalyst of support type and carries out hydrogenation reaction, obtains iso-amylene
Alcohol；It regenerates, recycles after catalyst inactivation；
The Al-Zn/CeO2 catalyst of the support type uses base metal Al and Zn as active component, can effectively improve
Isoamyl olefine aldehydr selective hydration prepares isoamyl olefine aldehydr conversion ratio, prenol selectivity and the yield in prenol reaction.
2. the method that isoamyl olefine aldehydr selective hydration according to claim 1 prepares prenol, which is characterized in that preferably
In the case of, the weight ratio of Al and Zn are 1:0.1~10；Preferably, the weight ratio of Al and Zn is 1:0.3-8；Regulate and control Al's and Zn
Weight ratio can preferably improve the conversion ratio of isoamyl olefine aldehydr and selectivity, the yield of prenol.
3. the method that isoamyl olefine aldehydr selective hydration according to claim 1 prepares prenol, the side of the catalyst
Method obtains catalyst precarsor this method comprises: (1) introduces compound containing Al and compound containing Zn in support C eO2；(2) will
The catalyst precarsor restores under hydrogen atmosphere, obtains the catalyst that isoamyl olefine aldehydr selective hydration prepares prenol.
4. the method that isoamyl olefine aldehydr selective hydration according to claim 3 prepares prenol, which is characterized in that preferably
Ground, on the basis of the total weight of catalyst, the content of Al is that the content of 1-25 weight %, Zn are 5-25 weight % and carrier
Content be 50-94 weight %；It is highly preferred that the content that the content of Al is 7-23 weight %, Zn is 5-20 weight %, Yi Jizai
The content of body is 57-88 weight %.
5. the method that isoamyl olefine aldehydr selective hydration according to claim 3 prepares prenol, it is characterised in that: preferably
Ground, the compound containing Al are at least one of aluminum nitrate, aluminium chloride, protochloride aluminium, nitric acid Asia aluminium；The compound containing Zn
The object of Zn can be changed under conditions of can obtaining catalyst precarsor and reduction in step (2) for carrier can be added
Matter；Under preferable case, the compound containing Zn is zinc chloride.
6. the method that isoamyl olefine aldehydr selective hydration according to claim 1 prepares prenol, it is characterised in that: described
The regeneration method of Al-Zn/CeO2 catalyst of support type be off into isoamyl olefine aldehydr raw material, oxygen is passed through, at 300 DEG C of temperature
~600 DEG C, 0.8~6.0MPa of pressure, oxygen volume space velocity be 100~1000h-1Under the conditions of made charcoal again to decaying catalyst
Raw 3~for 24 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643556A (en) * | 2019-08-23 | 2020-01-03 | 浙江工业大学 | Recombinant genetic engineering bacterium for co-expressing enal reductase and glucose dehydrogenase and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643556A (en) * | 2019-08-23 | 2020-01-03 | 浙江工业大学 | Recombinant genetic engineering bacterium for co-expressing enal reductase and glucose dehydrogenase and application thereof |
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