CN110292894A - A kind of tubular type continuous flow reaction unit and the method for preparing tert-butyl acetoacetate - Google Patents
A kind of tubular type continuous flow reaction unit and the method for preparing tert-butyl acetoacetate Download PDFInfo
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- CN110292894A CN110292894A CN201810236514.5A CN201810236514A CN110292894A CN 110292894 A CN110292894 A CN 110292894A CN 201810236514 A CN201810236514 A CN 201810236514A CN 110292894 A CN110292894 A CN 110292894A
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/46—Preparation of carboxylic acid esters from ketenes or polyketenes
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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
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Abstract
The present invention provides a kind of tubular type continuous flow reaction unit, the reaction unit includes: that alcohol measuring tank is connected by alcohol metering pump with catalyst mixing section, is connected with catalyst metering groove between alcohol measuring tank and catalyst mixing section；The other end of the catalyst mixing section is connected with tubular type continuous flow reactor respectively with ketene dimer measuring tank；The reactor other end is successively connect with condenser, surge tank and dnockout pumps, and pressure pump is equipped between tubular type continuous flow reactor and condenser, and surge tank is equipped with a transmission condenser.It additionally provides and has developed a kind of technique that tert-butyl acetoacetate is prepared using tubular type continuous flow reactor with the method present invention that the device prepare tert-butyl acetoacetate, greatly shorten reaction time, to reduce the generation of side reaction, improve product yield and content, thereby reduce the difficulty of rectifying separation, reduce production cost, and greatly reduces the security risk of production.
Description
Technical field
The present invention relates to chemical industry synthesis fields, and in particular to the preparation facilities and preparation method of tert-butyl acetoacetate.
Background technique
Tert-butyl acetoacetate
Alias: 3- butanone tert-butyl acrylate；The acetoacetic acid tert-butyl ester；
English name: tert-Butyl acetoacetate；
Dissolubility: being slightly soluble in water, is dissolved in dimethylbenzene；
Molecular formula: C8H14O3
Molecular weight: 158.195
Fusing point (DEG C): -38
Density (g/ml, 25/4 DEG C): 0.97
Effect and purposes: the raw material as medicine, pesticide, pigment is mainly used as acetyl second as organic synthesis intermediate
Acylating agent.In coatings industry, when for the acetoacetylated polyester of high solidification coating and other resin manufactures with hydroxyl
Non-catalytic method, make the hydroxyl in acetoacetyl displacement resin, effect can be such that resin viscosity reduces, dissolubility increase,
Glass transition point reduces, and increases bridging property, improves the caking property with metal, improves corrosion resistance, improves flexibility.
Mainly there are several types of routes for the prior art:
It 1) is to be synthesized using ester-interchange method, using ethyl acetoacetate or methyl acetoacetate is raw material in reflux shape
Ester exchange reaction is carried out with the tert-butyl alcohol under state, obtains finished product tert-butyl acetoacetate, the technological reaction time is long, and yield is low, most
In high yield it is 68%, and is related to the recycling of solvent toluene, it is at high cost；
2) it is Claisen ester condensation route, the tert-butyl alcohol is first prepared into sodium alkoxide, then carries out ester condensation again and obtain, acetyl
Tert-butyl acetate.The route needs to use expensive metallic sodium, and synthetic yield is low, and does not have mature industrialization report；
It 3) is that esterification is carried out using ketene dimer and the tert-butyl alcohol, having highest yield reported in the literature at present is 87%,
Yield is low, of poor quality, and the tertiary butyl ether of by-product is generated in reaction process, is affected to reaction yield.
Process above exist otherwise expensive raw material price or yield it is low, and be intermittent reaction, reaction time mistake
It is long, cause production preparation cost higher.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that, a kind of product yield is provided and content is high, at low cost, by-product
The device of the small continuous production tert-butyl acetoacetate of object, another technical problem are to provide a kind of tert-butyl acetoacetate
Production method.
The technical scheme is that a kind of tubular type continuous flow reaction unit, including pump and pipeline, the reaction unit packet
Include: alcohol measuring tank is connected by alcohol metering pump with catalyst mixing section, is connected between the alcohol measuring tank and catalyst mixing section
There is catalyst metering groove；The other end of the catalyst mixing section is reacted with a tubular type continuous flow respectively with ketene dimer measuring tank
Device is connected；
The tubular type continuous flow reactor other end is successively connect with condenser, surge tank and dnockout pumps, in the tubular type
It is equipped with pressure pump between continuous flow reactor and the condenser, a transmission condenser is equipped on the surge tank.
Wherein, the catalyst metering groove exit is equipped with catalyst dosing pump.
Wherein, the tubular type continuous flow reactor internal mix part cellular construction is SV type, SK type, SX type, SH type and SL
One of type；Wherein SV type unit is the cylindrical body assembled by the corrugated plating of certain specification；SK type unit is by one channel
The flight group of left and right torsion is welded；SX type unit constitutes many X-type units by the horizontal stripe intersected according to certain rules；SH type
Unit is made of double hole channel, and flight is placed in duct, and the orientation of adjacent cells double hole channel misplaces 90 °；SL type unit is by handing over
The horizontal stripe of fork constitutes single X-shaped unit according to certain rules.
Tubular type continuous flow reactor in the present invention, internal mix part structure is static mixer, and static mixer
Refer to that, without motor element in pipeline, only static original part can be divided into sv type, SK type etc..
A kind of technique preparing tert-butyl acetoacetate using above-mentioned reaction unit, including
A, the tert-butyl alcohol is added to by catalyst mixing section by alcohol metering pump first from alcohol measuring tank, is measured from catalyst
By catalyst dosing pump in slot, amines catalyst is also squeezed into catalyst mixing section, the dosage of amines catalyst accounts for reactant
The 0.03%~2% of gross mass；
B, after the two mixing, ketene dimer is added in starting ketene dimer metering pump, then squeezes into ketene dimer and alcoholic solution
Tubular type continuous flow reactor, reaction obtain thick ester, the mol ratio of ketene dimer and the tert-butyl alcohol are as follows: 1:1~1.4；Reaction temperature
It is 55~160 DEG C, reaction time is 0.5~60min, adjusts reaction pressure, reaction pressure 0 by pressure-regulating valve 9
~1MPa；
C, thick ester through condenser 10 is cooled to 30~65 DEG C after reaction, then flows into surge tank, and the low-boiling-point substance in thick ester is through saturating
Surge tank is back to after air-cooled condenser, fixed gas empties, and the thick ester in surge tank squeezes into rectifying column by dnockout pumps, and thick ester is through essence
After evaporating, the content of product is 99.0~99.5%, and product yield is 96~98%.
Preferably, it is reactor volume 1-2 that ketene dimer and alcoholic solution, which squeeze into the flow of tubular type continuous flow reactor,
When cubic meter, V (ketene dimer)=8.2~89.7L/min/m3, V (tert-butyl alcohol)=12.2~126.5L/min/m3。
The technique according to the present invention for preparing tert-butyl acetoacetate, it is preferred that the use of amines catalyst described in step a
Amount accounts for the 0.05~1.5% of reactant gross mass；The tert-butyl alcohol described in step a is molten condition.Tert-butyl alcohol molten condition is liquid
State is conducive to the mixing of reaction solution, is more advantageous to abundant reaction.It is further preferred that the dosage of catalyst described in step a accounts for reaction
The 0.05~0.25% of object gross mass.
The technique according to the present invention for preparing tert-butyl acetoacetate, it is preferred that ketene dimer described in step b and tertiary fourth
The mol ratio of alcohol is 1:1.01~1.2.
The technique according to the present invention for preparing tert-butyl acetoacetate, it is preferred that the amines catalyst be selected from propylamine,
One of butylamine, diethylamine, triethylamine, diethylenetriamine, aniline, diisopropylamine or more than one.
Further, the amines catalyst is one of diethylamine, triethylamine, aniline, diisopropylamine or one kind
More than.
During ketene dimer and the tert-butyl alcohol are esterified, since three methyl of the tert-butyl alcohol generate very large space steric hindrance
Effect affects the reactivity of molecule.The synthetic method is provided using one or more of organic amine catalyst, as ester
Change catalyst, reduce space steric effect during the reaction, improve the reactivity of molecule, to improve reaction speed
Rate and selectivity.Not only stability is good in this system for the catalyst of the type, and the later period is handled without independent, by common
The tert-butyl acetoacetate of high-quality can be obtained in rectifying；Tert-butyl acetoacetate is synthesized using the technique, ketene dimer turns
Rate reaches 100%, and product yield reaches 94% or more, and product content reaches 99% or more.
The technique according to the present invention for preparing tert-butyl acetoacetate, it is preferred that range of reaction temperature described in step b is
55~140 DEG C；Residence time ranges are 5~45min；Reaction pressure range is 0.02~0.6MPa.
The technique according to the present invention for preparing tert-butyl acetoacetate, it is preferred that the cooling temperature of thick ester described in step c
Range is 35~60 DEG C.
The present invention has studied a kind of technique that tert-butyl acetoacetate is prepared using tubular type continuous flow reactor, the tert-butyl alcohol with
After catalyst premixing, ketene dimer and its be sufficiently mixed in tubular reactor, under certain pressure and temperature, carry out
Continuous esterification greatly shortens reaction time compared with traditional batch technology, to reduce side reaction
It generates, improves product yield and content, thereby reduce the difficulty of rectifying separation, reduce production cost, and drop significantly
The security risk of low production.
The beneficial effects of the present invention are:
1) batch technology is changed to continuous flow process, shortens the reaction time, reduce the generation of side reaction, acetoacetate
The yield and content of the tert-butyl ester are improved；The conversion ratio of ketene dimer reaches 100%, and product yield reaches 96% or more, produces
Product content reaches 99% or more；
2) it is mixed into raw material hybrid reaction from raw material and catalyst, then to thick ester rectifying, entire technique is serialization behaviour
Make, technological operation easedization；
3) compared with intermittent reaction, tert-butyl acetoacetate is prepared using tubular type continuous flow reactor, the space of equipment accounts for
There is rate small, security risk is lower.
Detailed description of the invention
Fig. 1 is reaction system schematic diagram of the invention.
Fig. 2 is the reacting flow chart that process flow tubular reactor internal mix part cellular construction is SV type.
In figure, 1 is alcohol measuring tank, and 2 be ketene dimer measuring tank, and 3 be ketene dimer metering pump, and 4 be alcohol metering pump, and 5 are
Catalyst dosing pump, 6 be catalyst metering groove, and 7 be catalyst mixing section, and 8 be tubular type continuous flow reactor, and 9 are adjusted for pressure
Valve, 10 be condenser, and 11 be transmission condenser, and 12 be surge tank, and 13 be dnockout pumps.
Specific embodiment
Reaction system is as shown in Figure 1, reaction process is as shown in Figure 2.
Embodiment 1:
First from alcohol measuring tank 1 and catalyst metering groove 6, by metering pump 4 and 5, the tert-butyl alcohol and catalyst are distinguished
Flow by a certain percentage squeezes into catalyst mixing section 7 and starts ketene dimer metering pump 3, then make ketene dimer after the two mixing
Tubular type continuous flow reactor 8 is squeezed by certain flow with alcoholic solution, tubular reactor internal mix part cellular construction is SV type, institute
The mol ratio of the ketene dimer and the tert-butyl alcohol stated is 1:1.01, and catalyst is diethylamine, and it is total that the dosage of catalyst accounts for reactant
The 0.05% of quality, reaction temperature are 140 DEG C, reaction time 5min, adjust reaction pressure by pressure-regulating valve 9,
Reaction pressure is 0.6MPa, and thick ester is cooled to 35 DEG C through condenser 10 after reaction, then flows into surge tank 12, the low-boiling-point substance in thick ester
Surge tank 12 is back to after condenser 11, fixed gas empties, and the thick ester in surge tank 12 squeezes into rectifying column by metering pump 13,
Thick ester is after rectifying, and the content of product is 99.0%, product yield 96.0%.
Embodiment 2:
First from alcohol measuring tank 1 and catalyst metering groove 6, by metering pump 4 and 5, the tert-butyl alcohol and catalyst are distinguished
Flow by a certain percentage squeezes into catalyst mixing section 7 and starts ketene dimer metering pump 3, then make ketene dimer after the two mixing
Tubular type continuous flow reactor 8 is squeezed by certain flow with alcoholic solution, tubular reactor internal mix part cellular construction is SX type, institute
The mol ratio of the ketene dimer and the tert-butyl alcohol stated is 1:1.05, and catalyst is triethylamine, and it is total that the dosage of catalyst accounts for reactant
The 0.14% of quality, reaction temperature are 106 DEG C, reaction time 13min, adjust reaction pressure by pressure-regulating valve 9,
Reaction pressure is 0.36MPa, and thick ester is cooled to 40 DEG C through condenser 10 after reaction, then flows into surge tank 12, the low boiling in thick ester
Object is back to surge tank 12 after condenser 11, and fixed gas empties, and the thick ester in surge tank 12 squeezes into rectifying by metering pump 13
Tower, thick ester is after rectifying, and the content of product is 99.3%, product yield 96.7%.
Embodiment 3:
First from alcohol measuring tank 1 and catalyst metering groove 6, by metering pump 4 and 5, the tert-butyl alcohol and catalyst are distinguished
Flow by a certain percentage squeezes into catalyst mixing section 7 and starts ketene dimer metering pump 3, then make ketene dimer after the two mixing
Tubular type continuous flow reactor 8 is squeezed by certain flow with alcoholic solution, tubular reactor internal mix part cellular construction is SH type, institute
The mol ratio of the ketene dimer and the tert-butyl alcohol stated is 1:1.1, and catalyst is aniline, and the dosage of catalyst accounts for reactant gross mass
0.21%, reaction temperature be 120 DEG C, reaction time 20min, pass through pressure-regulating valve 9 adjust reaction pressure, reaction
Pressure is 0.28MPa, and thick ester is cooled to 45 DEG C through condenser 10 after reaction, then flows into surge tank 12, the low-boiling-point substance warp in thick ester
Surge tank 12 is back to after condenser 11, fixed gas empties, and the thick ester in surge tank 12 squeezes into rectifying column by metering pump 13, slightly
Ester is after rectifying, and the content of product is 99.4%, product yield 97.3%.
Embodiment 4:
First from alcohol measuring tank 1 and catalyst metering groove 6, by metering pump 4 and 5, the tert-butyl alcohol and catalyst are distinguished
Flow by a certain percentage squeezes into catalyst mixing section 7 and starts ketene dimer metering pump 3, then make ketene dimer after the two mixing
Tubular type continuous flow reactor 8 is squeezed by certain flow with alcoholic solution, tubular reactor internal mix part cellular construction is SL type, institute
The mol ratio of the ketene dimer and the tert-butyl alcohol stated is 1:1.2, and catalyst is diisopropylamine, and the dosage of catalyst accounts for reactant
The 1.5% of gross mass, reaction temperature are 55 DEG C, reaction time 55min, adjust reaction pressure by pressure-regulating valve 9,
Reaction pressure is 0.02MPa, and thick ester is cooled to 60 DEG C through condenser 10 after reaction, then flows into surge tank 12, the low boiling in thick ester
Object is back to surge tank 12 after condenser 11, and fixed gas empties, and the thick ester in surge tank 12 squeezes into rectifying by metering pump 13
Tower, thick ester is after rectifying, and the content of product is 99.5%, product yield 98%.
Embodiment 5:
First from alcohol measuring tank 1 and catalyst metering groove 6, by metering pump 4 and 5, the tert-butyl alcohol and catalyst are distinguished
Flow by a certain percentage squeezes into catalyst mixing section 7 and starts ketene dimer metering pump 3, then make ketene dimer after the two mixing
Tubular type continuous flow reactor 8 is squeezed by certain flow with alcoholic solution, tubular reactor internal mix part cellular construction is SL type, institute
The mol ratio of the ketene dimer and the tert-butyl alcohol stated is 1:1.1, and catalyst is the mixture of triethylamine and diisopropylamine, mixing
Ratio is m (triethylamine): m (diisopropylamine)=1:1, the dosage of catalyst account for the 0.7% of reactant gross mass, reaction temperature
It is 65 DEG C, reaction time 45min, reaction pressure, reaction pressure 0.04MPa, reaction is adjusted by pressure-regulating valve 9
Thick ester is cooled to 60 DEG C through condenser 10 afterwards, then flows into surge tank 12, and the low-boiling-point substance in thick ester is back to slow after condenser 11
Rush tank 12, fixed gas emptying, the thick ester in surge tank 12 squeezes into rectifying column by metering pump 13, thick ester after rectifying, product
Content is 99.5%, product yield 98%.
Embodiment 6:
First from alcohol measuring tank 1 and catalyst metering groove 6, by metering pump 4 and 5, the tert-butyl alcohol and catalyst are distinguished
Flow by a certain percentage squeezes into catalyst mixing section 7 and starts ketene dimer metering pump 3, then make ketene dimer after the two mixing
Tubular type continuous flow reactor 8 is squeezed by certain flow with alcoholic solution, tubular reactor internal mix part cellular construction is SH type, institute
The mol ratio of the ketene dimer and the tert-butyl alcohol stated is 1:1.05, and catalyst is the mixture of aniline, diethylamine and triethylamine, is mixed
Composition and division in a proportion example is m (aniline): m (diethylamine): m (triethylamine)=1:1:1, the dosage of catalyst account for the 0.3% of reactant gross mass,
Reaction temperature is 85 DEG C, reaction time 38min, adjusts reaction pressure by pressure-regulating valve 9, reaction pressure is
0.09MPa, thick ester is cooled to 60 DEG C through condenser 10 after reaction, then flows into surge tank 12, and the low-boiling-point substance in thick ester is through condenser
Surge tank 12 is back to after 11, fixed gas empties, and the thick ester in surge tank 12 squeezes into rectifying column by metering pump 13, and thick ester is through essence
After evaporating, the content of product is 99.5%, product yield 98%.
Present invention is generally directed to the reaction time in existing tert-butyl acetoacetate preparation process is too long, security risk is big, produces
The problems such as product yield and slightly lower content, has developed a kind of work that tert-butyl acetoacetate is prepared using tubular type continuous flow reactor
Skill greatly shortens reaction time, to reduce the generation of side reaction, improves product yield and content, in turn
The difficulty for reducing rectifying separation, reduces production cost, and greatly reduce the security risk of production.
Claims (10)
1. a kind of tubular type continuous flow reaction unit, including pump and pipeline, it is characterised in that: the reaction unit includes: alcohol metering
Slot is connected by alcohol metering pump with catalyst mixing section, is connected with catalyst gauge between the alcohol measuring tank and catalyst mixing section
Measuring tank；The other end of the catalyst mixing section is connected with a tubular type continuous flow reactor respectively with ketene dimer measuring tank；
The tubular type continuous flow reactor other end is successively connect with condenser, surge tank and dnockout pumps, continuous in the tubular type
It is equipped with pressure pump between flow reactor and the condenser, a transmission condenser is equipped on the surge tank.
2. tubular type continuous flow reaction unit according to claim 1, which is characterized in that the catalyst metering groove exit
Equipped with catalyst dosing pump.
3. tubular type continuous flow reaction unit according to claim 1, which is characterized in that in the tubular type continuous flow reactor
Portion's mixer element cellular construction is one of SV type, SK type, SX type, SH type and SL type；Wherein SV type unit is by certain specification
The cylindrical body that assembles of corrugated plating；SK type unit is welded by the flight group of the left and right torsion of one channel；SX type unit by
The horizontal stripe of intersection constitutes many X-type units according to certain rules；SH type unit is made of double hole channel, and flight is placed in duct,
The orientation of adjacent cells double hole channel misplaces 90 °；SL type unit constitutes single X-shaped unit by the horizontal stripe intersected according to certain rules.
4. a kind of method for preparing tert-butyl acetoacetate using reaction unit described in claim 1, it is characterised in that:
A, the tert-butyl alcohol is added to by catalyst mixing section by alcohol metering pump first from alcohol measuring tank, from catalyst metering groove
By catalyst dosing pump, amines catalyst is also squeezed into catalyst mixing section, the dosage of amines catalyst accounts for the total matter of reactant
The 0.03%~2% of amount；
B, after the two mixing, ketene dimer is added in starting ketene dimer metering pump, then ketene dimer and alcoholic solution is made to squeeze into tubular type
Continuous flow reactor, reaction obtain thick ester, the mol ratio of ketene dimer and the tert-butyl alcohol are as follows: 1:1~1.4；Reaction temperature is 55
~160 DEG C, reaction time be 0.5~60min, by pressure-regulating valve 9 adjust reaction pressure, reaction pressure be 0~
1MPa；
C, thick ester through condenser is cooled to 30~65 DEG C after reaction, then flows into surge tank, and the low-boiling-point substance in thick ester is condensed through transmission
Be back to surge tank after device, fixed gas emptying, the thick ester in surge tank squeezes into rectifying column by dnockout pumps, thick ester after rectifying,
The content of product is 99.0~99.5%, and product yield is 96~98%.
5. the method according to claim 4 for preparing tert-butyl acetoacetate, it is characterised in that: amine described in step a is urged
The dosage of agent accounts for the 0.05~1.5% of reactant gross mass；The tert-butyl alcohol described in step a is molten condition.
6. the method according to claim 4 for preparing tert-butyl acetoacetate, it is characterised in that: double ethylene described in step b
The mol ratio of ketone and the tert-butyl alcohol is 1:1.01~1.2.
7. the method according to claim 4 for preparing tert-butyl acetoacetate, it is characterised in that: the amines catalyst choosing
From one of propylamine, butylamine, diethylamine, triethylamine, diethylenetriamine, aniline, diisopropylamine or more than one.
8. the method according to claim 7 for preparing tert-butyl acetoacetate, it is characterised in that: the amines catalyst is
One of diethylamine, triethylamine, aniline, diisopropylamine or more than one.
9. the method according to claim 4 for preparing tert-butyl acetoacetate, it is characterised in that: react temperature described in step b
Spending range is 55~140 DEG C；Residence time ranges are 5~45min；Reaction pressure range is 0.02~0.6MPa.
10. the method according to claim 4 for preparing tert-butyl acetoacetate, it is characterised in that: thick ester described in step c
Cooling temperature range is 35~60 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045417A (en) * | 2019-12-29 | 2021-06-29 | 南通醋酸化工股份有限公司 | Process for producing acetoacetic ester by green catalytic method |
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