CN108144619A - It is a kind of to be used for catalyst and preparation method of the benzene carboxylic ester Hydrogenation for benzyl alcohol - Google Patents
It is a kind of to be used for catalyst and preparation method of the benzene carboxylic ester Hydrogenation for benzyl alcohol Download PDFInfo
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- CN108144619A CN108144619A CN201611098747.0A CN201611098747A CN108144619A CN 108144619 A CN108144619 A CN 108144619A CN 201611098747 A CN201611098747 A CN 201611098747A CN 108144619 A CN108144619 A CN 108144619A
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- benzene carboxylic
- carboxylic ester
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of benzene carboxylic ester Hydrogenation that is used for for catalyst of benzyl alcohol and preparation method thereof.Catalyst is made of four kinds of components of ambrose alloy zinc-aluminium, and in the total weight of catalyst, nickel accounts for 10wt%~30wt%, and copper accounts for 20wt%~50wt%, and zinc accounts for 20wt%~50wt%, and aluminium accounts for 5wt%~30wt%.Preparation method be by nickel, copper, zinc, aluminium solubility salt such as nitrate, it is dissolved in water in the ratio in its total weight in the catalyst, the mixed solution of four kinds of salt is made, then at certain temperature and stirring, pH=6~8 are neutralized to aqueous slkalis such as sodium hydroxide, ammonium hydroxide or carbonic acid sodium, generation precipitation precipitates filtered, washing, dry, roasting, molding.The catalyst can carry out for benzene carboxylic acid ester through hydrogenation under relatively low reaction temperature and pressure, and with higher conversion ratio and selectivity, so as to be conducive to save equipment investment and improve device security, improve production efficiency.
Description
Fields
The present invention relates to a kind of benzene carboxylic ester Hydrogenation that is used for for catalyst of benzyl alcohol and preparation method thereof
Technical background
Compound containing benzyl alcohol structure is a kind of important industrial chemicals.Benzyl alcohol is the weight of synthetic perfume, drug
Intermediate is wanted, and is had a wide range of applications in fields such as photosensitive, dyeing and finishing, cosmetics.Terephthalyl alcohol is in addition to being a kind of important
Organic synthesis intermediate, the cyclohexanedimethanol for continuing that hydrogen is added to obtain have important application in Material Field.Benzene first at present
There are mainly two types of the production methods of alcohol, and one kind is that benzyl chloride hydrolyzes to obtain benzyl alcohol, and another kind adds hydrogen or reduction to obtain for benzaldehyde
Benzyl alcohol.More salt by-product is had by benzyl chloride synthesizing benzoic alcohol to generate, and is not environmentally protective technique, and with benzaldehyde
It is expensive for raw material and uneconomical.Terephthalyl alcohol is made by paraxylene through chlorination, hydrolysis, to the corrosion resistance of equipment
The by-product generated in more demanding and production is more, limits large-scale production.Benzene carboxylic ester cheap and easy to get is application
Very extensive industrial chemicals.
The catalyst as used in ester through hydrogenation prepares alcohols has Ni-based, copper-based and manganese base etc., but these catalyst is anti-
Answer pressure higher, generally in more than 10MPa, even up to more than 25MPa, so high pressure can bring very high equipment
Investment, there is also some potential safety problemss.
The application of catalyst in the present invention can greatly reduce reaction pressure, while have higher conversion ratio and choosing
Selecting property has greatly saved the investment of equipment, while without the output of the by-products such as salt, has been conducive to increase economic efficiency, pacify
Full production.
Invention content
The object of the present invention is to provide a kind of benzene carboxylic ester Hydrogenations for the new catalyst and method of benzyl alcohol, can be with
It is carried out under relatively low reaction pressure, reduces pressure rating and the equipment investment of equipment, improve the safety and life of production
Produce efficiency.
It is a kind of for benzene carboxylic ester Hydrogenation for the catalyst of benzyl alcohol, be made of nickel-copper-four kinds of zinc-aluminium component,
In the total weight of catalyst, nickel accounts for 10wt%~30wt%, and copper accounts for 20wt%~50wt%, and zinc accounts for 20wt%~50wt%, aluminium
Account for 5wt%~30wt%.
It is a kind of for benzene carboxylic ester Hydrogenation for benzyl alcohol method, be by nickel, copper, zinc, aluminium solubility salt such as nitre
Hydrochlorate accounts for 10wt%~30wt% by nickel in its total weight in the catalyst, and copper accounts for 20wt%~50wt%, and zinc accounts for 20wt%
~50wt%, the ratio that aluminium accounts for 10wt%~30wt% are dissolved in water, and the mixed solution of four kinds of salt are made, then certain
At temperature and stirring, pH=6~8, generation precipitation are neutralized to aqueous slkalis such as ammonium hydroxide, sodium hydroxide or sodium carbonate, precipitation is passed through
Filter, washing, dry, roasting, molding.Drying temperature is 130 DEG C, 6 lab scale of drying time, and calcination temperature is 550 DEG C, the time 6
Hour.
Catalyst need to restore 4 hours in 400 DEG C~450 DEG C of hydrogen stream before use.
The application method of heretofore described benzene carboxylic ester Hydrogenation benzyl alcohol catalyst includes benzene carboxylic acid ester through hydrogenation mistake
Technical process and process conditions of journey etc..Hydrogenation process is：With pump by the solution of raw material benzene carboxylic ester squeeze into mixer with hydrogen
Gas mixes, and enters in hydrogenation reactor after preheated, is contacted in hydrogenation reactor with catalyst and hydrogenation reaction occurs, is catalyzed
Agent bed temperature is maintained at 200 DEG C~300 DEG C, and operating pressure is generally in 4.0MPa~8.0MPa, the reaction come out from reactor
Liquid enters gas-liquid separator, hydrogen compressed recycling again after cooling, and liquid send extraction product and recycling design.
Benzene carboxylic ester Hydrogenation is for the suitable condition of the reaction of benzyl alcohol：220 DEG C~300 DEG C of reaction temperature, reaction
Pressure 5.0MPa~8.0MPa, 0.1~0.5/h of air speed, more than 60% conversion ratio of raw material, the selectivity 95% of benzyl alcohol with
On.The analysis of raw material and product uses gas chromatograph, and chromatographic column is HP-5 capillary columns, 30 meters long, and carrier gas is nitrogen, FID
Detector.
Compared with the prior art, outstanding feature is the present invention：Active component nickel provided by the invention, copper, zinc and aluminium
The quaternary component catalyst of composition is raw material Hydrogenation for benzyl alcohol for benzene carboxylic ester, and reaction temperature is 200 DEG C~300
DEG C, reaction pressure 4.0MPa~8.0MPa.The temperature and pressure of the more common nickel-base catalyst of the process conditions substantially reduces, favorably
In saving equipment investment and improving safety, production efficiency is improved.
Specific embodiment
Embodiment 1：
31g nickel nitrates (Ni (NO3)2·6H2O), 45g copper nitrates (Cu (NO3)23H2O), 45g zinc nitrates (Zn
(NO3)2·6H2) and 37g aluminum nitrates (Al (NO O3)2·9H2O it) is dissolved in 500g hot distilled waters, at 85 DEG C, under stirring, uses matter
The ammonium hydroxide of amount concentration 28% is neutralized to pH=7, and the precipitation of generation is filtered, 6 hours dry at 130 DEG C after washing, 550 DEG C of roastings
It burns 6 hours, is then molded.Catalyst before use, restores 4 hours in 440 DEG C of hydrogen stream.
Embodiment 2
52g nickel nitrates (Ni (NO3)2·6H2O), 45g copper nitrates (Cu (NO3)2·3H2O), 35g zinc nitrates (Zn
(NO3)2·6H2) and 37g aluminum nitrates (Al (NO O3)2·9H2O it) is dissolved in 500g hot distilled waters, at 85 DEG C, under stirring, uses matter
The sodium hydroxide solution of amount concentration 25% is neutralized to pH=7, and the precipitation of generation is filtered, 6 hours dry at 130 DEG C after washing,
550 DEG C roast 6 hours, are then molded.Catalyst before use, restores 4 hours in 440 DEG C of hydrogen stream.
Embodiment 3
31g nickel nitrates (Ni (NO3)2·6H2O), 58g copper nitrates (Cu (NO3)2·3H2O), 40g zinc nitrates (Zn
(NO3)2·6H2) and 37g aluminum nitrates (Al (NO O3)2·9H2O it) is dissolved in 500g hot distilled waters, at 85 DEG C, under stirring, uses matter
Amount 20% sodium carbonate liquor of concentration is neutralized to pH=7, and the precipitation of generation is filtered, 6 hours dry at 130 DEG C after washing, and 550
DEG C roasting 6 hours, be then molded.Catalyst before use, restores 4 hours in 440 DEG C of hydrogen stream.
Embodiment 4
Reaction of the 10% methyl benzoate Hydrogenation of mass concentration for benzyl alcohol is carried out using catalyst prepared by embodiment 1
Experiment.Loaded catalyst is 10.0g, and experimental result is as follows.
Embodiment 5
It is standby to hexichol that the catalyst prepared using embodiment 2 carries out 5% dimethyl terephthalate (DMT) Hydrogenation of mass concentration
The reaction experiment of methanol.Loaded catalyst is 10.0g, and experimental result is as follows.
Embodiment 6
It is standby to hydroxyl first that the catalyst prepared using embodiment 3 carries out 10% methyl p-hydroxybenzoate Hydrogenation of mass concentration
The reaction experiment of base phenol.Loaded catalyst is 10.0g, and experimental result is as follows.
The catalyst can carry out for benzene carboxylic acid ester through hydrogenation under relatively low reaction temperature and pressure, and with higher
Conversion ratio and selectivity so as to be conducive to save equipment investment and improve device security, improve production efficiency.
Claims (10)
1. a kind of be used for catalyst of the benzene carboxylic ester Hydrogenation for benzyl alcohol, it is characterised in that：It is by nickel-copper-four kinds of zinc-aluminium group
Be grouped as, in the total weight of catalyst, nickel accounts for 10wt%~30wt%, and copper accounts for 20wt%~50wt%, zinc account for 20wt%~
50wt%, aluminium account for 5wt%~30wt%.
2. according to catalyst described in claim 1, it is characterised in that：In the total weight of catalyst, nickel preferably accounts for 28%, and copper is excellent
Choosing accounts for 37%, and zinc preferably accounts for 25%, and aluminium preferably accounts for 10%.
3. for benzene carboxylic ester Hydrogenation for the preparation method of the catalyst of benzyl alcohol, feature described in a kind of claims 1 or 2
It is：Be by nickel, copper, zinc, aluminium solubility salt, be dissolved in water in its required ratio, be made four kinds of salt mixed solution,
Then under stirring condition, pH=6~8 are neutralized to aqueous slkali, generation precipitation, precipitation is filtered, washing, dry, roasting, into
Type.
4. preparation method described in accordance with the claim 3, it is characterised in that：Drying temperature is 130~140 DEG C, drying time 6~
8 hours, calcination temperature was 500~550 DEG C, and the time is 6~8 hours.
5. preparation method described in accordance with the claim 3, it is characterised in that：Soluble-salt is nitrate.
6. preparation method described in accordance with the claim 3, it is characterised in that：Aqueous slkali is in ammonium hydroxide, sodium hydroxide or sodium carbonate
One or two or more kinds.
7. catalyst described in a kind of claims 1 or 2 is in benzene carboxylic ester Hydrogenation for the application in benzyl alcohol.
8. according to the application described in claim 7, it is characterised in that：Catalyst before use need to be in 400 DEG C~450 DEG C of hydrogen
It is restored 4~5 hours in stream.
9. according to the application described in claim 7, it is characterised in that：Benzene carboxylic ester Hydrogenation is suitable for the reaction of benzyl alcohol
Condition is：220 DEG C~300 DEG C of reaction temperature, reaction pressure 5.0MPa~8.0MPa, 0.1~0.5/h of air speed.
10. according to the application described in claim 7, it is characterised in that：Benzene carboxylic ester is methyl benzoate, terephthalic acid (TPA) diformazan
One or two or more kinds in ester, methyl p-hydroxybenzoate, the mass concentration 3~20% of benzene carboxylic ester.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611098747.0A CN108144619A (en) | 2016-12-04 | 2016-12-04 | It is a kind of to be used for catalyst and preparation method of the benzene carboxylic ester Hydrogenation for benzyl alcohol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611098747.0A CN108144619A (en) | 2016-12-04 | 2016-12-04 | It is a kind of to be used for catalyst and preparation method of the benzene carboxylic ester Hydrogenation for benzyl alcohol |
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| CN108144619A true CN108144619A (en) | 2018-06-12 |
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| CN201611098747.0A Pending CN108144619A (en) | 2016-12-04 | 2016-12-04 | It is a kind of to be used for catalyst and preparation method of the benzene carboxylic ester Hydrogenation for benzyl alcohol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569602A (en) * | 2018-12-06 | 2019-04-05 | 吉林大学 | A kind of Cu/MxOy/Al2O3Catalyst, preparation method and its preparing the application in benzyl alcohol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054060A (en) * | 1989-12-21 | 1991-08-28 | 联合碳化化学品及塑料有限公司 | With the hydrogenation that copper-aluminium-other metal catalyst carries out |
| CN102476056A (en) * | 2012-02-28 | 2012-05-30 | 浙江嘉化能源化工股份有限公司 | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof |
-
2016
- 2016-12-04 CN CN201611098747.0A patent/CN108144619A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054060A (en) * | 1989-12-21 | 1991-08-28 | 联合碳化化学品及塑料有限公司 | With the hydrogenation that copper-aluminium-other metal catalyst carries out |
| CN102476056A (en) * | 2012-02-28 | 2012-05-30 | 浙江嘉化能源化工股份有限公司 | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569602A (en) * | 2018-12-06 | 2019-04-05 | 吉林大学 | A kind of Cu/MxOy/Al2O3Catalyst, preparation method and its preparing the application in benzyl alcohol |
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Application publication date: 20180612 |