CN107827712A - A kind of production method of verdox synthetic perfume - Google Patents
A kind of production method of verdox synthetic perfume Download PDFInfo
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- CN107827712A CN107827712A CN201711041536.8A CN201711041536A CN107827712A CN 107827712 A CN107827712 A CN 107827712A CN 201711041536 A CN201711041536 A CN 201711041536A CN 107827712 A CN107827712 A CN 107827712A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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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
- C07C29/17—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
- C07C29/19—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 in six-membered aromatic rings
- C07C29/20—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 in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention discloses a kind of production method of verdox synthetic perfume, petroleum ether, phenol, sulfuric acid are added to reactor, 100~150 DEG C are warming up to after the tert-butyl alcohol is added dropwise, the oil reservoir of mixed reaction solution is put into alkali cleaning stirred tank, water layer adds petroleum ether, and the oil reservoir after layering is also placed in alkali cleaning stirred tank；Alkali cleaning stirred tank is hydrogenated with after sodium hydroxide solution water washed reservoir again, oil reservoir after layering is transferred to hydrogenation reaction kettle, hydrogenation reaction is carried out by palladium-carbon catalyst, the first still distillation tower is sent to after reacting liquid filtering, the verdol of collection is transferred to reaction kettle of the esterification, adds acetic anhydride, p-methyl benzenesulfonic acid heating response, and kettle liquid is delivered to oil reservoir after washing kettle is hydrogenated with sodium hydroxide solution after distillation and washed again by reaction solution, oil reservoir is transferred to rectifying column, collects verdox product.Its raw material is easy to get, and product yield is high, and final products content is up to more than 98.5%, and cis-isomer content reaches more than 85% in product.
Description
Technical field
The present invention relates to the production method of synthetic perfume, and in particular to a kind of verdox synthetic perfume
Production method.
Background technology
Verdox, also known as ortho position iris ester, chemical name are acetic acid 2- (1,1- dimethyl ethyl) ring
Own ester, English name：o-Tert-butyl cyclohexyl acetate.Acetic acid o-tert-butyl ring is not found in nature
The presence of own ester.Molecular formula C12H22O2, No. CAS：88-41-5, outward appearance is to be colourless to pale yellow transparent oily liquids or solid knot
Crystalline substance, fusing point are about 35 DEG C, have citrus type fruity fragrance as fresh bergamot and limette, and have the banksia rose of pine and cypress sample fragrant
Adjust, can be used in polytype essence, particularly in perfumed soap and detergent perfumer.Verdox it is relative
Density（25℃）：0.9390~0.9460, refraction index（20℃）：1.4490~1.4550,221 DEG C of boiling point（94~95 DEG C/
1.0kPa）, it is dissolved in the organic solvents such as ethanol, ethylene glycol, it is not soluble in water.Verdox is that cis and trans are different
The mixture of structure body, the fragrance of cis-isomer is more stronger than transisomer, the verdox of high-cis
Cis-isomer accounting reach more than 90%, can be widely applied in various compositions, particularly in the fragrance of a flower and banksia rose odor type
Essence in purposes it is preferable.
Verdox has the fragrant and similar jasmine fragrance and iris of the strong fragrance of a flower, the banksia rose, apple
The fragrance of sample, property is highly stable, not easy to change, is a kind of conventional synthetic perfume, particularly useful in whole modern perfume,
Warm feature can be injected for floral perfume, costustoot essence.It is widely used in perfume fragrance, cosmetic essence and fragrance for detergents
In being formulated Deng daily chemical essence, it can stablize in most of essence products and use, can almost be used in all daily essence products
In, or even it can also be played a role in bleaching agent, can be with iris ester, bergamio, terpinyl acetate, ionyl acetate
Fragrance merges very well, including perfume, face cream, anhidrotic, deodorant, shampoo, perfumed soap, washing powder, dish washing agent, liquid bleach,
Fabric softening agent, deodorant spray, cleanser etc., especially for washing powder, perfumed soap, cologne, shampoo, face cream and face
Especially useful in frost, dosage can determine the dosage that use 10% or so according to different purposes, and maximum dose can reach 30%,
IFRA does not limit regulation.
Verdox is one of important widely used synthetic perfume, demand in recent years by
Flaring is big, and general production method is using phenol as initiation material, using sulfuric acid or lewis acid as catalyst, is passed through isobutene gas
Being alkylated turns into o-tert-butylphenol, then turns into verdol with raney ni catalysis hydrogenation, finally uses acetic acid again
Esterification obtains verdox, and this method processing step is various, and product yield is low, causes production cost higher, and
It is difficult to control with the process conditions of isobutene gas and phenol reactant, produces substantial amounts of acetic acid waste water during esterification, it is difficult to is returned
Receive and utilize.
The content of the invention
In order to solve the deficiency of generally existing in the existing production process route of verdox, the present invention provides
A kind of production method using phenol and the tert-butyl alcohol as initiation material synthesis of acetic acid o-tert-butyl cyclohexyl, its raw material are easy to get, product
Yield is high, and final products content is up to more than 98.5%, and cis-isomer content reaches more than 85% in product, so that final production
The aroma of pure of product is soft, meets the requirement of essence and flavoring agent blending.
The production method of the verdox synthetic perfume of the present invention, comprises the following steps：
a）Petroleum ether is first added into reactor and reduces temperature to 0~15 DEG C, then phenol is slowly added into reactor, remains anti-
0~15 DEG C of kettle is answered, is stirred 1~3 hour；
b）Sulfuric acid is slowly added into reactor, continues to temperature of reaction kettle at 0~15 DEG C；
c）The tert-butyl alcohol is added dropwise into reactor, time for adding controls at 4~12 hours, after completion of dropwise addition, reactor is warming up to
100~150 DEG C, continue stirring 4~8 hours, when phenol content in mass≤0.5% when, terminate reaction；
d）O-tert-butylphenol caused by reactor and p-t-butyl phenol mixed reaction solution are delivered in stirred tank, stands and divides
Layer, oil reservoir is put into alkali cleaning stirred tank, and petroleum ether is added in water layer, is stirred 1~3 hour, stratification, the oil reservoir is also put
Enter into alkali cleaning stirred tank；
e）The sodium hydroxide solution that mass fraction is 5% is added into alkali cleaning stirred tank, stratification after stirring 1~3 hour, is gone
Except alkali lye layer, oil reservoir adds clear water, and stratification after stirring 1~3 hour, oil reservoir is transferred in hydrogenation reaction kettle；
f）Palladium-carbon catalyst is put into hydrogenation reaction kettle, closed hydrogenation reaction kettle, is replaced again with hydrogen with after nitrogen displacement, is risen
Temperature to 80~150 DEG C, keep reaction pressure 2.0Mpa, 5~15 hours reaction time, when o-tert-butylphenol content in mass
When≤0.5%, terminate reaction；
g）Verdol caused by hydrogenation reaction kettle and patchone mixed reaction solution are sent into filter to enter
Row filtering, filter liquid phase filtrate are sent to the distillation still of the first still distillation tower；
h）Under normal pressure, the distillation still of the first still distillation tower is warming up to 60~90 DEG C, reclaims petroleum ether, and petroleum ether recovery terminates
Afterwards, in 100~110 DEG C of kettle temperature, 90~95 DEG C of tower top temperature, 1000~1333Pa pressure, enter under the conditions of reflux ratio 1: 1~1: 12
Row fractionation, the verdol of collection are transferred to reaction kettle of the esterification；
i）Acetic anhydride is added into reaction kettle of the esterification, then puts into p-methyl benzenesulfonic acid, turn on agitator, opens steam valve to esterification
Reactor is heated, 80~150 DEG C of controlling reaction temperature, 5~15 hours reaction time, and reaction solution is transferred to the steaming of the second autoclave
In the distillation still for evaporating tower；
j）Under normal pressure, the distillation still of the second still distillation tower is warming up to 100~120 DEG C, recovery of acetic acid, after acetic acid recovery terminates,
Distillation still kettle liquid delivers to washing kettle；
k）The sodium hydroxide solution that mass fraction is 5% is added to washing kettle, stratification after stirring 1~3 hour, removes alkali lye
Layer, oil reservoir add clear water and washed, and stratification after stirring 1~3 hour, oil reservoir is transferred to the rectifying still of autoclave rectifying column
In；
l）In 100~150 DEG C of rectifying still kettle temperature, 105~110 DEG C of tower top temperature, 1000~1333Pa pressure, reflux ratio 1: 1~1
: it is fractionated under the conditions of 12, collects verdox product；
Described step a）The dosage of petrochina ether and the mass ratio of phenol are the ︰ 1 of 1.0 ︰ 1~5.0；Described step b）Middle sulphur
The mass ratio of the dosage of acid and petroleum ether and phenol total amount of feeding is the ︰ 5% of 1 ︰ 0.5% ~ 1；Described step c）The middle tert-butyl alcohol
Dosage and the mol ratio of phenol are the ︰ 1 of 1.0 ︰ 1~5.0；Described step d）The inventory of petrochina ether and the mass ratio of water layer
For the ︰ 1 of 0.5 ︰ 1~2；Described step e）The inventory of middle sodium hydroxide solution and the mass ratio of reaction solution oil reservoir be 0.2 ︰ 1~
2 ︰ 1, the inventory of clear water and the mass ratio of reaction solution oil reservoir are the ︰ 1 of 0.5 ︰ 1~2；Described step i）The dosage of middle acetic anhydride
Mol ratio with verdol is the ︰ 1 of 1.0 ︰ 1~5.0, dosage and acetic anhydride and the o-tert-butyl ring of p-methyl benzenesulfonic acid
The mass ratio of hexanol total amount of feeding is the ︰ 5% of 1 ︰ 0.5%~1；Described step k）The inventory and distillation still of middle sodium hydroxide solution
The mass ratio of kettle liquid is the ︰ 1 of 0.2 ︰ 1~2, and the inventory of clear water and the mass ratio of distillation still kettle liquid oil reservoir are the ︰ 1 of 0.5 ︰ 1~2.
Preferably, described step a）The dosage of petrochina ether and the mass ratio of phenol are the ︰ 1 of 2.0 ︰ 1~2.5, described
Step b）The mass ratio of the dosage of middle sulfuric acid and petroleum ether and phenol total amount of feeding is 1 ︰ 1%~1 ︰ 2%, described step c）
The dosage of the middle tert-butyl alcohol and the mol ratio of phenol are 1.0 ︰ 1~1.5 ︰ 1, described step d）The inventory and water of petrochina ether
The mass ratio of layer is 0.5 ︰ 1~1 ︰ 1, described step e）The inventory of middle sodium hydroxide solution and the mass ratio of reaction solution oil reservoir
For the ︰ 1 of 0.2 ︰ 1~0.5, the inventory of clear water and the mass ratio of reaction solution oil reservoir are the ︰ 1 of 0.5 ︰ 1~1；Described step i）Middle vinegar
The dosage of acid anhydrides and the mol ratio of verdol are the ︰ 1 of 1.5 ︰ 1~2.0, the dosage and acetic anhydride of p-methyl benzenesulfonic acid
Mass ratio with verdol total amount of feeding is the ︰ 2.0% of 1 ︰ 1.0%~1；Described step k）Middle sodium hydroxide solution
The mass ratio of inventory and distillation still kettle liquid is the ︰ 1 of 0.2 ︰ 1~0.5, the inventory of clear water and the mass ratio of distillation still kettle liquid oil reservoir
For the ︰ 1 of 0.5 ︰ 1~1.
Described step f）Middle hydrogenation reaction kettle material is stainless steel, and the palladium content of palladium-carbon catalyst is 5% in mass,
The inventory of palladium-carbon catalyst and the volumetric ratio of hydrogenation reaction kettle are 0.002~0.02Kg/ L.
Described step i）The material of middle reaction kettle of the esterification is enamel.
Described step g）In the first still distillation tower and step i）In the second still distillation Ta Tanei filling cy500 it is stainless
Steel ripple packing, described step k）Filling cy700 stainless steel ripple packings in middle autoclave rectifying tower.
Advantages of the present invention is embodied in：
1st, after being alkylated reaction as initiation material using phenol and the tert-butyl alcohol, then hydrogenated rear and acetic anhydride acetylization reaction is given birth to
Produce verdox, raw material is easy to get, and yield is high, o-tert-butylphenol caused by phenol and tert-butyl alcohol reaction with to uncle
The accounting of butylphenol reaches 7 ︰ 3, accessory substance p-t-butyl phenol is hydrogenated and esterification after can obtain iris ester product and be subject to
Utilize；
2nd, using petroleum ether as alkylated reaction and the organic solvent of hydrogenation reaction, overcome reacted in hydrogenation process not exclusively with
And catalyst apply mechanically after the shortcomings that inactivating, while can omit common alkylated reaction using dichloroethanes as solvent when steaming
Evaporate processing step；
3rd, verdol and acetic anhydride carry out acetylization reaction, produce byproduct acetic acid recoverable, and general
The production technology of verdol and acetic acid esterified reaction production verdox, produces substantial amounts of acetic acid and gives up
Water.
Embodiment
Embodiment
1）First 150kg petroleum ethers are measured by head tank, are added in 500L enamel reaction stills, turn on agitator and cold
Freeze salt solution valve, reactor is reduced into temperature to 15 DEG C.
2）Phenol 72kg is slowly added into reactor, 15 DEG C of maintenance reaction kettle, is stirred 2 hours, then it is high-order by sulfuric acid
Groove metered sulfuric acid 5kg into reactor.
3）Temperature of reaction kettle is continued at 15 DEG C, by tert-butyl alcohol head tank by the way that pump is added dropwise, uncle is added dropwise into reactor
Butanol 70kg, time for adding control at 6~8 hours, after completion of dropwise addition, close chilled brine valve, by reactor heat up 100~
120 DEG C, continue stirring 4~8 hours, sampling is detected, and when phenol content≤0.5%, cooling, terminates reaction.
4）Caused o-tert-butylphenol and p-t-butyl phenol mixed reaction solution are stirred by material pumping to bottom is bored
In kettle, stratification 2 hours.Oil reservoir is put into alkali cleaning stirred tank.Addition petroleum ether 50kg in water layer, turn on agitator,
Stirring 2 hours, stratification, oil reservoir is put into alkali cleaning stirred tank, and water layer is discharged into Sewage Disposal and handled.
5）The metered clear water 950kg into sodium hydroxide stirred tank, then from hand hole into sodium hydroxide stirred tank
Quantitative sodium hydroxide 50kg is put into, turn on agitator, 5% sodium hydroxide solution is prepared, is driven into sodium hydroxide solution head tank
In.
6）By sodium hydroxide solution head tank, measured into alkali cleaning stirred tank, add 5% sodium hydroxide solution 75kg, open
Agitator is opened, alkali cleaning is carried out to the oil reservoir of collection, after stirring 2 hours, stratification 2 hours, alkali lye layer, squeezed into by product pump
Next batch is carried out to alkali liquid high-level groove to apply mechanically.Oil reservoir adds clear water 170kg and washed, after stirring 2 hours, stratification
2 hours, oil reservoir was transferred in hydrogenation reaction kettle, and water layer is discharged into Sewage Disposal and handled.
7）5% palladium-carbon catalyst 5kg is quantitatively disposably put into hydrogenation reaction kettle, closed hydrogenation reaction kettle, is entered with nitrogen
Line replacement 4~6 times, nitrogen is then charged with to pressure 2.0Mpa, after system pressure is stable, enter line replacement 4~6 times with hydrogen,
It is then charged with hydrogen, regulation hydrogenation reaction kettle pressure to 2.0Mpa.
8）After system pressure is stable, hydrogen gas valve is closed, is warming up to 100~110 DEG C, reaction system pressure balance
Afterwards, hydrogen valve is opened, is kept for reaction pressure 2.0Mpa, 5~15 hours reaction time, after reacting 5 hours, at interval of 2 hours
Sampling carries out chromatogram detection, when o-tert-butylphenol content≤0.5%, terminates reaction, pressure release.
9）Caused verdol and patchone mixed reaction solution are sent to essence using nitrogen pressure
Close filter is filtered.Filter liquid phase filtrate is sent to the distillation still of still distillation tower, filter solid catalysis with nitrogen
Agent squeezes into accurate filter with petroleum ether by membrane pump, and recoil is washed till in hydrogenation reaction kettle, carries out lower batch hydrogenation reaction.
10）Open steam valve to heat up to distillation still, under normal pressure, at 60~90 DEG C of kettle temperature, reclaim petroleum ether, treat tower
Terminate to reclaim petroleum ether when top temperature decline or zero discharge.The petroleum ether of recovery is driven into petroleum ether head tank using product pump
Applied mechanically.It is then turned on vavuum pump, at 100~105 DEG C of kettle temperature, 90~95 DEG C of tower top temperature, 1000~1333Pa pressure, backflow
Carry out collecting verdol under fractionation conditions under the conditions of than 1: 1~1: 12, the verdol of collection is transferred to
Reaction kettle of the esterification, distillation still kettle liquid are that patchone delivers to patchone head tank using nitrogen pressure, can
Production for iris ester.
11）By acetic anhydride head tank into reaction kettle of the esterification metered acetic anhydride 70kg, then by hand hole to reaction
P-methyl benzenesulfonic acid 3.5kg is put into kettle, turn on agitator, steam valve is opened and reaction kettle of the esterification is heated, control reaction
100~120 DEG C of temperature, in 8~10 hours reaction time, reaction solution is transferred in the distillation still of still distillation tower.
12）Open steam valve to heat up to distillation still, under normal pressure, at 100~120 DEG C of kettle temperature, recovery of acetic acid, treat tower
Terminate recovery of acetic acid when top temperature decline or zero discharge.The acetic acid of recovery is driven into acetic acid head tank using product pump, distillation
Kettle kettle liquid delivers to washing kettle using nitrogen pressure.
13）From sodium hydroxide solution head tank, the metered 5% sodium hydroxide solution 30kg into washing kettle, stirring is opened
Device, after stirring 2 hours, stratification 2 hours, alkali lye layer, alkali liquid high-level groove is driven into by product pump and carries out next batch set
With.Oil reservoir adds clear water 120kg and washed, and after stirring 2 hours, stratification 2 hours, oil reservoir is transferred to autoclave rectifying column
Rectifying still in, water layer is discharged into Sewage Disposal and handled.
14）Open steam valve to heat up to distillation still, at 100~150 DEG C of kettle temperature, vavuum pump is opened, in tower top temperature
105~110 DEG C of degree, 1000~1333Pa pressure, carry out under the conditions of reflux ratio 1: 1~1: 12 collecting acetic acid uncle neighbour under fractionation conditions
Butylcyclohexyl ester product, when tower top temperature decline or zero discharge, terminate rectifying, cooling, press kettle residual.
Made product is colourless transparent liquid, has fruity and banksia rose fragrance, is through gas chromatographic analysis product purity
99.06%, wherein cis-isomer accounting 87.9%, detect refraction index（20℃）For 1.4517, relative density（25℃）For
0.9410。
Product checking GC conditions are：Chromatographic column HP-5（30m x 0.32mm x 0.25um）；Detector FID, temperature 280
℃；Sample introduction：Sample size about 0.2ul, split ratio 1：100,250 DEG C of injector temperature；Carrier gas：N2, flow velocity 20L/min, press before post
34.47kPa；Chromatograph oven temperature：For linear temperature program from 150 DEG C~230 DEG C, speed is 4 DEG C/min, retains 10min.
The amount of each raw material of the present invention can also be：Step 1）The dosage of petrochina ether and the mass ratio of phenol are 1.0 ︰ 1
~5.0 ︰ 1；Step 2）The mass ratio of the dosage of middle sulfuric acid and petroleum ether and phenol total amount of feeding is the ︰ 5% of 1 ︰ 0.5% ~ 1；Step
3）The dosage of the middle tert-butyl alcohol and the mol ratio of phenol are the ︰ 1 of 1.0 ︰ 1~5.0；Step 4）The inventory of petrochina ether and water layer
Mass ratio is the ︰ 1 of 0.5 ︰ 1~2；Step 6）The inventory of middle sodium hydroxide solution and the mass ratio of reaction solution oil reservoir be 0.2 ︰ 1~
2 ︰ 1, the inventory of clear water and the mass ratio of reaction solution oil reservoir are the ︰ 1 of 0.5 ︰ 1~2；Step 7）The inventory of middle palladium-carbon catalyst with
The volumetric ratio of hydrogenation reaction kettle is 0.002~0.02Kg/ L；Step 11）The dosage and verdol of middle acetic anhydride
Mol ratio be the ︰ 1 of 1.0 ︰ 1~5.0, dosage and the acetic anhydride and the matter of verdol total amount of feeding of p-methyl benzenesulfonic acid
It is the ︰ 5% of 1 ︰ 0.5%~1 to measure ratio；Step 13）The inventory of middle sodium hydroxide solution and the mass ratio of distillation still kettle liquid be 0.2 ︰ 1~
2 ︰ 1, the inventory of clear water and the mass ratio of distillation still kettle liquid oil reservoir are the ︰ 1 of 0.5 ︰ 1~2.
Claims (5)
1. a kind of production method of verdox synthetic perfume, comprises the following steps：
a）Petroleum ether is first added into reactor and reduces temperature to 0~15 DEG C, then phenol is slowly added into reactor, remains anti-
0~15 DEG C of kettle is answered, is stirred 1~3 hour；
b）Sulfuric acid is slowly added into reactor, continues to temperature of reaction kettle at 0~15 DEG C；
c）The tert-butyl alcohol is added dropwise into reactor, time for adding controls at 4~12 hours, after completion of dropwise addition, reactor is warming up to
100~150 DEG C, continue stirring 4~8 hours, when phenol content in mass≤0.5% when, terminate reaction；
d）O-tert-butylphenol caused by reactor and p-t-butyl phenol mixed reaction solution are delivered in stirred tank, stands and divides
Layer, oil reservoir is put into alkali cleaning stirred tank, and petroleum ether is added in water layer, is stirred 1~3 hour, stratification, the oil reservoir is also put
Enter into alkali cleaning stirred tank；
e）The sodium hydroxide solution that mass fraction is 5% is added into alkali cleaning stirred tank, stratification after stirring 1~3 hour, is gone
Except alkali lye layer, oil reservoir adds clear water, and stratification after stirring 1~3 hour, oil reservoir is transferred in hydrogenation reaction kettle；
f）Palladium-carbon catalyst is put into hydrogenation reaction kettle, closed hydrogenation reaction kettle, is replaced again with hydrogen with after nitrogen displacement, is risen
Temperature to 80~150 DEG C, keep reaction pressure 2.0Mpa, 5~15 hours reaction time, when o-tert-butylphenol content in mass
When≤0.5%, terminate reaction；
g）Verdol caused by hydrogenation reaction kettle and patchone mixed reaction solution are sent into filter to enter
Row filtering, filter liquid phase filtrate are sent to the distillation still of the first still distillation tower；
h）Under normal pressure, the distillation still of the first still distillation tower is warming up to 60~90 DEG C, reclaims petroleum ether, and petroleum ether recovery terminates
Afterwards, in 100~110 DEG C of kettle temperature, 90~95 DEG C of tower top temperature, 1000~1333Pa pressure, enter under the conditions of reflux ratio 1: 1~1: 12
Row fractionation, the verdol of collection are transferred to reaction kettle of the esterification；
i）Acetic anhydride is added into reaction kettle of the esterification, then puts into p-methyl benzenesulfonic acid, turn on agitator, opens steam valve to esterification
Reactor is heated, 80~150 DEG C of controlling reaction temperature, 5~15 hours reaction time, and reaction solution is transferred to the steaming of the second autoclave
In the distillation still for evaporating tower；
j）Under normal pressure, the distillation still of the second still distillation tower is warming up to 100~120 DEG C, recovery of acetic acid, after acetic acid recovery terminates,
Distillation still kettle liquid delivers to washing kettle；
k）The sodium hydroxide solution that mass fraction is 5% is added to washing kettle, stratification after stirring 1~3 hour, removes alkali lye
Layer, oil reservoir add clear water and washed, and stratification after stirring 1~3 hour, oil reservoir is transferred to the rectifying still of autoclave rectifying column
In；
l）In 100~150 DEG C of rectifying still kettle temperature, 105~110 DEG C of tower top temperature, 1000~1333Pa pressure, reflux ratio 1: 1~1
: it is fractionated under the conditions of 12, collects verdox product；
Described step a）The dosage of petrochina ether and the mass ratio of phenol are the ︰ 1 of 1.0 ︰ 1~5.0；Described step b）Middle sulphur
The mass ratio of the dosage of acid and petroleum ether and phenol total amount of feeding is the ︰ 5% of 1 ︰ 0.5% ~ 1；Described step c）The middle tert-butyl alcohol
Dosage and the mol ratio of phenol are the ︰ 1 of 1.0 ︰ 1~5.0；Described step d）The inventory of petrochina ether and the mass ratio of water layer
For the ︰ 1 of 0.5 ︰ 1~2；Described step e）The inventory of middle sodium hydroxide solution and the mass ratio of reaction solution oil reservoir be 0.2 ︰ 1~
2 ︰ 1, the inventory of clear water and the mass ratio of reaction solution oil reservoir are the ︰ 1 of 0.5 ︰ 1~2；Described step i）The dosage of middle acetic anhydride
Mol ratio with verdol is the ︰ 1 of 1.0 ︰ 1~5.0, dosage and acetic anhydride and the o-tert-butyl ring of p-methyl benzenesulfonic acid
The mass ratio of hexanol total amount of feeding is the ︰ 5% of 1 ︰ 0.5%~1；Described step k）The inventory and distillation still of middle sodium hydroxide solution
The mass ratio of kettle liquid is the ︰ 1 of 0.2 ︰ 1~2, and the inventory of clear water and the mass ratio of distillation still kettle liquid oil reservoir are the ︰ 1 of 0.5 ︰ 1~2.
2. a kind of production method of verdox synthetic perfume according to claim 1, it is characterized in that：Institute
The step a stated）The dosage of petrochina ether and the mass ratio of phenol are 2.0 ︰ 1~2.5 ︰ 1, described step b）Middle sulfuric acid is matched somebody with somebody
The mass ratio of doses and petroleum ether and phenol total amount of feeding is 1 ︰ 1%~1 ︰ 2%, described step c）The dosage of the middle tert-butyl alcohol with
The mol ratio of phenol is 1.0 ︰ 1~1.5 ︰ 1, described step d）The inventory of petrochina ether and the mass ratio of water layer are 0.5 ︰ 1
~1 ︰ 1, described step e）The inventory of middle sodium hydroxide solution and the mass ratio of reaction solution oil reservoir are the ︰ 1 of 0.2 ︰ 1~0.5, clearly
The inventory of water and the mass ratio of reaction solution oil reservoir are the ︰ 1 of 0.5 ︰ 1~1；Described step i）The dosage of middle acetic anhydride and adjacent uncle
The mol ratio of butylcyclohexyl alcohol is the ︰ 1 of 1.5 ︰ 1~2.0, and the dosage and acetic anhydride and verdol of p-methyl benzenesulfonic acid are total
The mass ratio of inventory is the ︰ 2.0% of 1 ︰ 1.0%~1；Described step k）The inventory of middle sodium hydroxide solution and distillation still kettle liquid
Mass ratio be the ︰ 1 of 0.2 ︰ 1~0.5, the inventory of clear water and the mass ratio of distillation still kettle liquid oil reservoir are the ︰ 1 of 0.5 ︰ 1~1.
3. a kind of production method of verdox synthetic perfume according to claim 1, it is characterized in that：
Described step f）Middle hydrogenation reaction kettle material is stainless steel, and the palladium content of palladium-carbon catalyst is 5% in mass, palladium carbon catalysis
The inventory of agent and the volumetric ratio of hydrogenation reaction kettle are 0.002~0.02Kg/ L.
4. a kind of production method of verdox synthetic perfume according to claim 1, it is characterized in that：Institute
The step i stated）The material of middle reaction kettle of the esterification is enamel.
5. a kind of production method of verdox synthetic perfume according to claim 1,2,3 or 4, its
It is characterized in：Described step g）In the first still distillation tower and step i）In the second still distillation Ta Tanei filling cy500 it is stainless
Steel ripple packing, described step k）Filling cy700 stainless steel ripple packings in middle autoclave rectifying tower.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111203217A (en) * | 2020-03-11 | 2020-05-29 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method and application thereof in p-tert-butylphenol hydrogenation |
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| CN111203217B (en) * | 2020-03-11 | 2022-08-05 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method and application thereof in p-tert-butylphenol hydrogenation |
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