CN106083527A - A kind of preparation method of amylalcohol - Google Patents
A kind of preparation method of amylalcohol Download PDFInfo
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- CN106083527A CN106083527A CN201610471484.7A CN201610471484A CN106083527A CN 106083527 A CN106083527 A CN 106083527A CN 201610471484 A CN201610471484 A CN 201610471484A CN 106083527 A CN106083527 A CN 106083527A
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- amylalcohol
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- valeraldehyde
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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
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation method of a kind of amylalcohol, comprise the steps: to continue through valeraldehyde, water, the material of mixed solvent composition and be filled with the fixed bed of catalyst and carry out hydration reaction and produce reactant liquor, reaction temperature is 200 DEG C, and reaction pressure is 5MPa, and volume space velocity is 0.5hr‑1；The reactant liquor obtained in step 1) cooling is layered as oil phase and aqueous phase, rectification under oil phase material normal pressure, and the fraction condensation of 20 30 DEG C obtains unreacted valeraldehyde, and the fraction condensation collection of 80 120 DEG C obtains semi-finished product amylalcohol；Take semi-finished product amylalcohol and be added thereto to sodium hydroxide, after shaking, stratification, discard water layer, filter organic layer, retain filtrate.The present invention uses technique scheme, valeraldehyde conversion ratio is up to 99.9%, obtain amylalcohol purity up to 99.99%, energy consumption is low, can reduce manufacturing cost, on the premise of ensureing conversion ratio and purity, technique is simple, by-product is few, pollution-free, and the safety of technique is high, the preparation method of amylalcohol free from corrosion to equipment.
Description
Technical field
The present invention relates to chemical technology field, concretely relate to a kind of method utilizing valeraldehyde to prepare amylalcohol.
Background technology
Valeraldehyde, is a kind of colourless liquid, calls valeral, be slightly soluble in water, be dissolved in ethanol, ether, belong to inflammable thing, mainly
Purposes is Hydrogenation amylalcohol and aoxidizes valeric acid processed, also serves as spice, organic synthesis intermediate, rubber accelerator.
Valeraldehyde hydrogenation is a kind of main method preparing amylalcohol, and existing preparation method conversion ratio is only 80-90%,
The shortcomings such as purity can only achieve 96%, there is energy consumption high simultaneously, and the at high temperature easy efflorescence of catalyst, coking, regeneration difficulty,
Still the industrialized mass production requirement of isovaleral can not be met.
Summary of the invention
The technical problem to be solved in the present invention be for the deficiencies in the prior art provide a kind of valeraldehyde conversion ratio up to
99.9%, obtain amylalcohol purity up to 99.99%, energy consumption is low, can reduce manufacturing cost, is ensureing
On the premise of conversion ratio and purity, technique is simple, and by-product is few, pollution-free, and the safety of technique is high, corrosion-free to equipment
The preparation method of amylalcohol.
For solving the above-mentioned technical problem present invention by the following technical solutions: the preparation method of a kind of amylalcohol, including as follows
Step:
1), valeraldehyde, water, the material of mixed solvent composition are continued through it is filled with the fixed bed of catalyst to carry out hydration anti-
Should produce reactant liquor, reaction temperature is 200 DEG C, and reaction pressure is 5MPa, and volume space velocity is 0.5hr-1；
2), by the reactant liquor obtained in step 1) cool down and be layered as oil phase and aqueous phase, rectification under oil phase material normal pressure, 20-30 DEG C
Fraction condensation obtain unreacted valeraldehyde, the fraction condensation collection of 80-120 DEG C obtains semi-finished product amylalcohol；
3), take semi-finished product amylalcohol and be added thereto to sodium hydroxide, after shaking, stratification, discard water layer, filter organic layer,
Retain filtrate；
4) the adsorbent post that, the filtrate of gained in step 3) be passed through dress aluminium oxide carries out adsorption treatment；
5), in described step 4), filtrate with 0.5-30 column volume/hour speed flow through the adsorbent post equipped with aluminium oxide；
6), the amylalcohol after absorption is carried out rectification, obtain refined amylalcohol.
The following is further improvement of the present invention:
In step 1), valeraldehyde, water, the weight ratio of mixed solvent are 3:2:1.
Improve further:
In step 1), the consumption of catalyst accounts for the 0.1% of total material.
Improve further:
Described catalyst is made up of the material of following weight portion: molybdenum oxide 5 parts, cobalt oxide 6 parts, tungsten oxide 3 parts, nickel oxide 3
Part, potassium oxide 4 parts, six ammonium chloropalladates 8 parts, white carbon black 3 parts, Pulvis Talci 6 parts, 8 parts of molecular sieve, amorphous silica-alumina 10 parts；
The preparation method of above-mentioned catalyst, comprises the steps:
1), by above-mentioned molybdenum oxide 5 parts, cobalt oxide 6 parts, tungsten oxide 3 parts, nickel oxide 3 parts, potassium oxide 4 parts, six ammonium chloropalladates 8
Part, white carbon black 3 parts, Pulvis Talci 6 parts, 8 parts of molecular sieve, 10 parts of mix homogeneously of amorphous silica-alumina, compressing, obtain complex catalyst precursor
Body；
2), adding in plasma daughter generator by catalyst precursor in step 1, the power adjusting plasma generator is
Carry out plasma-activated during 50-1000W, and plasma activation time is 3～40min；
Step 2) cavity of plasma generator is metallic cavity or glass chamber；Exciting electrode is low frequency electrode, penetrates
Frequently electrode or microwave electrodes；
Step 2) in, when described catalyst precursor is inserted described plasma generator, first that hydrogenation catalyst is uniform
Be placed in the container that electric conductivity is good, container is placed in plasma generator, opens vacuum pump, at plasma
The vacuum of 10-50Pa is formed in the vacuum cavity of generator；
Step 2) described in the exciting electrode of plasma generator be radio-frequency electrode, radio-frequency electrode power is 60-100W.
The present invention uses technique scheme, valeraldehyde conversion ratio up to 99.9%, obtain amylalcohol purity up to
99.99%, energy consumption is low, can reduce manufacturing cost, and on the premise of ensureing conversion ratio and purity, technique is simple, by-product
Few, pollution-free, the safety of technique is high, the preparation method of amylalcohol free from corrosion to equipment.
Detailed description of the invention
Embodiment, the preparation method of a kind of amylalcohol, comprise the steps:
1), valeraldehyde, water, the material of mixed solvent composition are continued through it is filled with the fixed bed of catalyst to carry out hydration anti-
Should produce reactant liquor, reaction temperature is 200 DEG C, and reaction pressure is 5MPa, and volume space velocity is 0.5hr-1 。
2), the reactant liquor obtained in step 1) cooling is layered as oil phase and aqueous phase, rectification under oil phase material normal pressure, 20-
The fraction condensation of 30 DEG C obtains unreacted valeraldehyde, and the fraction condensation collection of 80-120 DEG C obtains semi-finished product amylalcohol；
3), take semi-finished product amylalcohol and be added thereto to sodium hydroxide, after shaking, stratification, discard water layer, filter organic layer,
Retain filtrate；
4) the adsorbent post that, the filtrate of gained in step 3) be passed through dress aluminium oxide carries out adsorption treatment；
5), in described step 4), filtrate with 0.5-30 column volume/hour speed flow through the adsorbent post equipped with aluminium oxide；
6), the amylalcohol after absorption is carried out rectification, obtain refined amylalcohol.
In step 1), valeraldehyde, water, the weight ratio of mixed solvent are 3:2:1.
In step 1), mixed solvent is made up of the onitrophenol that weight ratio is 5:1 and positive butanone.
In step 1), the consumption of catalyst accounts for the 0.1% of total material.
Described catalyst is made up of the material of following weight portion: molybdenum oxide 5 parts, cobalt oxide 6 parts, tungsten oxide 3 parts, oxidation
3 parts of nickel, potassium oxide 4 parts, six ammonium chloropalladates 8 parts, white carbon black 3 parts, Pulvis Talci 6 parts, 8 parts of molecular sieve, amorphous silica-alumina 10 parts.
Described molecular sieve is Y type molecular sieve, β zeolite, ZSM-2 molecular sieve and the mixture of SAPO-11 molecular sieve, Y
The mass ratio of type molecular sieve, β zeolite, ZSM-5 molecular sieve and SAPO-11 molecular sieve is 5:3:2:1.
The relative crystallinity of described SAPO-11 molecular sieve is 98%, and crystal particle diameter is 2.5 μm.
The relative crystallinity 95%～110% of described Y type molecular sieve, crystal particle diameter is 1.8 μm.
Described amorphous silica-alumina comprises silicon oxide 8wt%-50wt%, and specific surface area is 700-800m2/ g, pore volume is
1.6-1.8ml/g, bore dia 8-15nm, shared pore volume accounts for the 95%-98% of total pore volume, and infrared total acid content is 0.30-
0.45mmol/g, middle strong acid amount/infrared total acid content is 0.56-0.81, and L acid amount/B acid amount is 1.40-2.30.
The preparation method of amorphous silica-alumina described above is as follows:
A, respectively preparation sodium aluminate solution and sodium silicate solution；
B, by sodium aluminate solution adds part or all of sodium silicate solution, then pass to CO2Gas, controlling reaction temperature is
10-40 DEG C, the pH value controlling cemented into bundles is 8-11；Wherein as the CO being passed through2 Gas flow accounts for the 40% of total intake
～100%, add excess silicon acid sodium solution；
C, at the control temperature and pH value of step b, the mixture of step b gained ventilates and stablizes 40-60 minute；
D, the solidliquid mixture of step c gained is filtered, Cake Wash；
E, the filter cake of step d gained is pulled an oar, then carry out hydrothermal treatment consists, through filtering, being dried, obtain amorphous silica-alumina；Institute
The hydrothermal conditions stated is as follows: at 120-150 DEG C, processes 2-5 hour under 0.5-4.0MPa water vapor pressure.
In step b, as the CO being passed through2When gas flow accounts for the 50%-80% of total intake, add surplus
Remaining sodium silicate solution.
In described step a, the concentration of sodium aluminate solution is 15-55g Al2O3/ l, sodium silicate solution dense
Degree is 50-200g SiO2/l。
Step b adds all or part of sodium silicate solution, is whole sodium silicate solutions of being added
5wt%-100wt%.
Described CO2The concentration of gas is 30v%-60v%.
The detailed process employing following methods of step b:
(1), in sodium aluminate, add whole sodium silicate after, be passed through CO2Gas；
(2), in sodium aluminate, after addition part sodium silicate, it is passed through whole CO2Gas, then adds excess silicon in mixture
Acid sodium solution；
(3), in sodium aluminate, after addition part sodium silicate, it is passed through part CO2Gas, more logical CO2Gas is while adding
Enter excess silicon acid sodium solution.
Washing described in step d is that 50-90 DEG C of deionized water of filter cake is washed till neutrality.
Making beating described in step e is to be 8:1-10:1 by solid-liquid volume ratio, and add water in filter cake making beating.
Drying condition described in step e is as follows: dry 6-8 hour at 110-130 DEG C.
The preparation method of above-mentioned Y type molecular sieve includes following process: fresh NaY Crystallization of Zeolite serosity is filtering
Rinsing molecular sieve filter cake with the alkali liquor of molecular sieve butt quality 4-6 times during separation, concentration of lye is 0.001-0.5mol/L, alkali
Liquid temp is 30-90 DEG C；Then above-mentioned NaY molecular sieve filter cake is pulled an oar, adds the compound solution containing H+ ion,
The pH value making NaY molecular sieve pulp is maintained at 2.5-7.0, and reaction temperature is 5-100 DEG C, exchange reaction 0.2-6
Hour, swap with the sodium in zeolite with H+, after H+ exchange, have filtration, washing, roasting process.
The preparation method of above-mentioned catalyst, comprises the steps:
1), by above-mentioned molybdenum oxide 5 parts, cobalt oxide 6 parts, tungsten oxide 3 parts, nickel oxide 3 parts, potassium oxide 4 parts, six ammonium chloropalladates 8
Part, white carbon black 3 parts, Pulvis Talci 6 parts, 8 parts of molecular sieve, 10 parts of mix homogeneously of amorphous silica-alumina, compressing, obtain complex catalyst precursor
Body；
2), adding in plasma daughter generator by catalyst precursor in step 1, the power adjusting plasma generator is
Carry out plasma-activated during 50-1000W, and plasma activation time is 3～40min；
Step 2) cavity of plasma generator is metallic cavity or glass chamber；Exciting electrode is low frequency electrode, penetrates
Frequently electrode or microwave electrodes；
Step 2) in, when described catalyst precursor is inserted described plasma generator, first that hydrogenation catalyst is uniform
Be placed in the container that electric conductivity is good, container is placed in plasma generator, opens vacuum pump, at plasma
The vacuum of 10-50Pa is formed in the vacuum cavity of generator；
Step 2) described in the exciting electrode of plasma generator be radio-frequency electrode, radio-frequency electrode power is 60-100W.
Claims (4)
1. the preparation method of an amylalcohol, it is characterised in that: comprise the steps:
1), valeraldehyde, water, the material of mixed solvent composition are continued through it is filled with the fixed bed of catalyst to carry out hydration anti-
Should produce reactant liquor, reaction temperature is 200 DEG C, and reaction pressure is 5MPa, and volume space velocity is 0.5hr-1；
2), by the reactant liquor obtained in step 1) cool down and be layered as oil phase and aqueous phase, rectification under oil phase material normal pressure, 20-30 DEG C
Fraction condensation obtain unreacted valeraldehyde, the fraction condensation collection of 80-120 DEG C obtains semi-finished product amylalcohol；
3), take semi-finished product amylalcohol and be added thereto to sodium hydroxide, after shaking, stratification, discard water layer, filter organic layer,
Retain filtrate；
4) the adsorbent post that, the filtrate of gained in step 3) be passed through dress aluminium oxide carries out adsorption treatment；
5), in described step 4), filtrate with 0.5-30 column volume/hour speed flow through the adsorbent post equipped with aluminium oxide；
6), the amylalcohol after absorption is carried out rectification, obtain refined amylalcohol.
The preparation method of amylalcohol the most according to claim 1, it is characterised in that: in step 1), valeraldehyde, water, mixing are molten
The weight ratio of agent is 3:2:1.
The preparation method of amylalcohol the most according to claim 1, it is characterised in that: in step 1), the consumption of catalyst accounts for always
The 0.1% of material.
The preparation method of amylalcohol the most according to claim 1, it is characterised in that: described catalyst is by the thing of following weight portion
Matter forms: molybdenum oxide 5 parts, cobalt oxide 6 parts, tungsten oxide 3 parts, nickel oxide 3 parts, potassium oxide 4 parts, six ammonium chloropalladates 8 parts, white carbon black
3 parts, Pulvis Talci 6 parts, 8 parts of molecular sieve, amorphous silica-alumina 10 parts；
The preparation method of above-mentioned catalyst, comprises the steps:
1), by above-mentioned molybdenum oxide 5 parts, cobalt oxide 6 parts, tungsten oxide 3 parts, nickel oxide 3 parts, potassium oxide 4 parts, six ammonium chloropalladates 8
Part, white carbon black 3 parts, Pulvis Talci 6 parts, 8 parts of molecular sieve, 10 parts of mix homogeneously of amorphous silica-alumina, compressing, obtain complex catalyst precursor
Body；
2), adding in plasma daughter generator by catalyst precursor in step 1, the power adjusting plasma generator is
Carry out plasma-activated during 50-1000W, and plasma activation time is 3-40min；
Step 2) cavity of plasma generator is metallic cavity or glass chamber；
Step 2) in, when described catalyst precursor is inserted described plasma generator, first by hydrogenation catalyst equably
It is placed in the container that electric conductivity is good, container is placed in plasma generator, opens vacuum pump, send out at plasma
The vacuum of 10-50Pa is formed in the vacuum cavity of raw device；
Step 2) described in the exciting electrode of plasma generator be radio-frequency electrode, radio-frequency electrode power is 60-100W.
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| CN201610471484.7A CN106083527A (en) | 2016-06-27 | 2016-06-27 | A kind of preparation method of amylalcohol |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3980718A (en) * | 1971-01-13 | 1976-09-14 | Yeda Research & Development Co. Ltd. | Production of alcohols by reduction of carbonyl compounds with a crystalline aluminosilicate-isopropanol system |
| CN101185893A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Catalyst for preparation of decyl alcohols by gas-phase hydrogenation of decylenaldehydes and preparation method thereof |
| CN101376104A (en) * | 2007-08-31 | 2009-03-04 | 赢创奥克森诺有限责任公司 | Hydrogenation catalyst and method for the production of alcohols by hydrogenating carbonyl compounds |
| KR101219258B1 (en) * | 2009-10-08 | 2013-01-10 | 주식회사 엘지화학 | Method For The Hydrogenation Of Aldehydes And Apparatus Using The Same |
-
2016
- 2016-06-27 CN CN201610471484.7A patent/CN106083527A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3980718A (en) * | 1971-01-13 | 1976-09-14 | Yeda Research & Development Co. Ltd. | Production of alcohols by reduction of carbonyl compounds with a crystalline aluminosilicate-isopropanol system |
| CN101185893A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Catalyst for preparation of decyl alcohols by gas-phase hydrogenation of decylenaldehydes and preparation method thereof |
| CN101376104A (en) * | 2007-08-31 | 2009-03-04 | 赢创奥克森诺有限责任公司 | Hydrogenation catalyst and method for the production of alcohols by hydrogenating carbonyl compounds |
| KR101219258B1 (en) * | 2009-10-08 | 2013-01-10 | 주식회사 엘지화학 | Method For The Hydrogenation Of Aldehydes And Apparatus Using The Same |
Non-Patent Citations (1)
| Title |
|---|
| CHANGJUN LIU等: "Plasma methods for preparing green catalysts: Current status and perspective", 《CHINESE JOURNAL OF CATALYSIS》 * |
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