CN107141239B - A kind of method of bisphenol synthesis S in supergravity reactor - Google Patents
A kind of method of bisphenol synthesis S in supergravity reactor Download PDFInfo
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- CN107141239B CN107141239B CN201710271862.1A CN201710271862A CN107141239B CN 107141239 B CN107141239 B CN 107141239B CN 201710271862 A CN201710271862 A CN 201710271862A CN 107141239 B CN107141239 B CN 107141239B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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Abstract
The method of bisphenol synthesis S, is related to organic synthesis field in a kind of supergravity reactor.Including hypergravity sulfonating reaction system, hypergravity at sulfone reaction system, Liquid liquid Separation system, condensing reflux system, crystal system.With supergravity reactor as sulfonation, at sulfone reactor, sulfonation process and the mass transfer at sulfone process, heat transfer are greatly enhanced, the microcosmic mixing of reaction is enhanced, reacts more thorough, the product purity of preparation is higher；Supergravity reactor, which is used, at sulfone system adds condensation division box, the method for having built hypergravity point hydraulic art bisphenol synthesis S；Selection mesitylene is solvent.Sulfonating reaction temperature is 100 DEG C, is 165 DEG C at sulfone reaction temperature, and the reaction time is 1~2 hour, obtains crude product bisphenol S into solvent removal is crossed, and 15~20% ethanol water washing is added, and crystallisation by cooling obtains product.The low product of purity is high, 2,4 ' content of isomer can be obtained in the method for the present invention, and product yield is up to 86%.
Description
Technical field
The present invention relates to organic synthesis fields.More particularly, to a kind of hypergravity bisphenol synthesis S new method.
Background technique
Bisphenol S is a kind of organic intermediate that purposes is very extensive, is applied to many necks such as fuel, drug, pesticide, auxiliary agent
Domain.The one kind of bisphenol S as color developing agent in thermosensitive color development recording sheet, in view of its high temperature resistant, plasticity is strong, oil resistance is higher etc.
Advantage is increasingly becoming mainstream color developing agent in the industrial production.Current domestic about 200,000 tons of the demand to bis-phenol color developing agent/
Year, but production capacity is only 3600 tons/year, largely needs import, and domestic market notch is huge.The synthetic method of bisphenol S at this stage
And its that there are problems is as described below: using 4,4 '-dichloro diphenyl sulfone Hydrolyze methods, reaction obtains 4 in alkaline environment, 4 '-BPS's
Sodium salt, then react to obtain 4 in acidic environment, 4 '-BPS.The method simple process is convenient, but 4,4 '-dichloro diphenyl sulfone price of raw material
Valuableness, high production cost.In addition, the reaction has to carry out under the conditions of alkali fusion, it is required that harsher.Therefore the life is used
It is relatively difficult to reach a large amount of preparation 4,4'-BPS to produce route.Using sulfide oxidation method, process flow is 4,4'- dihydroxy two
Diphenyl sulfide is in H2O24,4'-BPS and H is generated under oxidation2O.Key point in the process flow is intermediate 4,4'- dihydroxy
The synthesis of base diphenyl sulfide, due to intermediate 4,4'- dihydroxy diphenyl sulfide raw material sources are less, expensive, and operate
Due to being related to the inconvenient using danger of sulfur dichloride in journey, it is not suitable for industrializing large-scale production.Using sulfonation evaporation,
Using phenol as raw material, the concentrated sulfuric acid or sulfur trioxide are sulfonating agent, by sulfonating reaction synthetic intermediate p-hydroxybenzenyl sulfonate, in turn
Dehydration synthesis 4,4'-BPS and by-product 2,4'-BPS under the high temperature conditions.The raw material used in the process flow is phenol and dense
Sulfuric acid is all base stock, and manufacturing cost is low and raw material is easy to get, therefore the country mostly uses the method to prepare bisphenol S.
Bisphenol S preparation process generally uses phenol-sulphoacid system method of sulfonating, relates generally to sulfonating reaction and anti-at sulfone
It answers, sulfonating reaction belongs to fast response, belongs to long response time at sulfone reaction, and reaction process needs timely separation product water, otherwise easily
Lead to that side reaction occurs.Using traditional stirred-tank reactor, exist to separate most of bisphenol S production process in time at present
The problems such as moisture, undercompounding, lead to that product yield is low, conversion ratio is low, reaction-separation mismatch problem.Accordingly, of the invention
Using advantage of the high-gravity technology in terms of strengthening microcosmic mixing, propose using overweight reactor as reaction unit, using anti-
The technique for answering-dividing water to combine improves bisphenol S product quality and production process efficiency with this, formed hypergravity react-divide water system
Standby bisphenol S new technology.The present invention selects supergravity reactor first to synthesize p-hydroxybenzenyl sulfonate as sulfonation reactor, then to hydroxyl
Base benzene sulfonic acid, phenol are raw material, the bisphenol synthesis S in supergravity reactor.By removing process, subtractive process obtains product
Bisphenol S.
High-gravity technology is the new technology for strengthening mass transfer, mixing and chemical reaction, which is rotated using hypergravity
The centrifugal force that bed inner rotator rotation generates simulates Elevated Gravity to strengthen transmitting and reaction process, and transmitting is significantly increased
With the efficiency of reaction process, hypergravity swinging bed device mainly includes closed shell, inside has the rotor of a rotation, on rotor
There is ring packing layer, different fluids flows into revolving bed from the corresponding entrance of shell, the centrifugal force field in the packing layer of rotation
Under (i.e. Elevated Gravity) carry out mass transport process, mass transfer rate than in traditional each reactor improve 1~3 order of magnitude.To rotation
The general understanding that rotated bed strengthens mass transport process principle is: fluid is torn into tiny drop, brin under centrifugal force field environment
Or liquid film, the surface area largely quickly updated is generated, significantly reinforcing mass transfer and mixed process.Using the technology, can strengthen
To spread the sulfonating reaction of control.In addition, supergravity reactor is small in size, it is easily installed, industrial application has natural
Advantage.
Summary of the invention
In place of avoiding above-mentioned the deficiencies in the prior art, a kind of synthetic method of bisphenol S is provided.Choosing
Selecting large chemical products is raw material, using supergravity reactor as sulfonation, at sulfone reactor, efficiently solves sulfonation process heat
The technical issues of effect is strong, system viscosity increase leads to poor fluidity, proposes that supergravity reactor divides modified starch bisphenol S, solves
It has determined the unmatched problem of reaction-separation, the present invention synthesizes that purity is high, color be good, product of high income.It provides a kind of overweight
Power is reacted-is divided water and prepares bisphenol S new method, prepared with effective solution face during bisphenol S cannot and time-division water, Bu Nengti
For good mixing, cause the yield of bisphenol S lower, the not high problem of purity.Use reflux water-dividing device will in reaction process
At the timely dispensing system of water generated in sulfone reaction process, supergravity reactor is combined with reflux water-dividing, improves bisphenol S
Yield and purity.This preparation process is base stock, including two sets of hypergravity reaction systems from big comprehensive chemicals, realizes intermediate
It is synthesized to the preparation process of product synthesis and solvent recovery.Solvent recovering system improves the service life of solvent, improves
The utilization rate of solvent, reduces solvent usage, reduces discharge amount；The sulfone reaction time is shortened into simultaneously, reduces equipment ruler
It is very little.Realize efficient, environmentally friendly, the inexpensive preparation of high-purity bisphenols S.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
A kind of hypergravity prepares the device of bisphenol S, including hypergravity sulfonating reaction system, hypergravity at sulfone reaction system,
Liquid liquid Separation system is condensed back system, crystal system；Process flow is as shown in the picture: phenol and mesitylene feed pot (1)
It is connect by valve, pump with the first supergravity reactor (10) feed inlet, concentrated sulfuric acid feed pot (2) passes through valve, pump and first
The connection of supergravity reactor (10) feed inlet；First supergravity reactor (10) liquid outlet and the first stirred reactor (11) are even
It connects, the first stirred reactor (11) is connect by valve, pump with the first supergravity reactor (10) feed inlet, and hypergravity sulphur is formed
Change reaction cycle circuit；First stirred reactor (11) is connected by valve, pump and the feed inlet of the second supergravity reactor (16)
It connects, the feed inlet of the second supergravity reactor (16) also passes through valve, pump and concentrated sulfuric acid feed pot (2) and connects, the second hypergravity
The liquid outlet of reactor (16) is connect with the second stirred reactor (17), and the second stirred reactor (17) passes through pump, valve and the
The feed inlet of two supergravity reactors (16) connects, and forms hypergravity into sulfone reaction cycle circuit；Second supergravity reactor
(16) it is additionally provided with gas vent, gas vent is connect with water diversion system (24), and water diversion system (24) can separate the water that reaction generates；
Second stirred reactor (17) is connected by pump, valve and Liquid liquid Separation system (25) feed inlet, Liquid liquid Separation system (25)
One discharge port is connect with washing and crystal system (26), another discharge port and phenol and equal three of Liquid liquid Separation system (25)
Toluene feed pot (1) connection.
Water diversion system (24) is condensing reflux system.
The method that bisphenol S is prepared using above-mentioned apparatus, which is characterized in that phenol is molten in a heated condition with mesitylene
Solution is added phosphorous acid, is pumped into the first supergravity reactor by pump, and centre controls flow by flowmeter；The concentrated sulfuric acid simultaneously
It is pumped into the first supergravity reactor (10) by pump；Sulfonating reaction starts, by adjust supergravity reactor motor revolving speed,
In supergravity reactor water leg the flow of the temperature of cooling medium and reactive material controls reaction temperature, and control valve is controlled
Internal circulating load in hypergravity sulfonating reaction circulation loop processed, carries out sulfonating reaction in this cyclic process；First is stirred to react
Solution in device (11) is pumped into the second supergravity reactor, by supplementing phenol and part constantly into the second supergravity reactor
Solvent, at occurring to react at sulfone in the second supergravity reactor of sulfone system, the second stirred reactor, water diversion system (24) is separated
The water generated at sulfone reaction；Mesitylene is removed by Liquid liquid Separation system (25) and is recycled to phenol and mesitylene feed pot
(1) in, product material flows into washing, crystal system (26) is washed.
The method of bisphenol synthesis S, the synthetic method operating procedure are as follows in further preferred supergravity reactor:
1) intermediate-p-hydroxybenzenyl sulfonate synthesis:
Phenol is added in mesitylene, and temperature control is added phosphorous acid, is pumped into the first supergravity reactor at 65 DEG C, dense
Sulfuric acid is pumped into the first supergravity reactor, and constant 100 DEG C of temperature, circular response 25min, aging 30min；Further preferred benzene
The molar ratio of phenol and mesitylene is (0.8-1.5): 1, the molar ratio of the concentrated sulfuric acid and phenol is (1-1.5): 1, every 100g-150g
4g phosphorous acid is added in mesitylene；
2) synthesis of bisphenol S:
The phenol of synthesis moderate with p-hydroxybenzenyl sulfonate is pumped into the second supergravity reactor, by water leg
Thermal medium regulation is 165 DEG C at sulfone temperature, is opened water diversion system (such as condensed moisture water system), circular response 2 hours, and liquid separation is de-
Water removal, mesitylene is simultaneously back to the second supergravity reactor, the product that Liquid liquid Separation system (25) is isolated through cooling, wash
It washs, crystallize and obtain bisphenol S.
Present invention process is combined with stirred tank reactor using supergravity reactor as synthetic intermediate para hydroxybenzene sulphur
Acid and product bisphenol S, which is effectively utilized the efficient mass transfer performance of supergravity reactor, while utilizing stirred tank
Reactor, which provides, reacts the necessary residence time.Reflux water-dividing technique is used in the synthesis unit of bisphenol S, bis-phenol can be improved
S conversion ratio.The technique effectively improves mass-transfer efficiency in bisphenol S synthesis process and is asked by the conversion ratio of Equilibrium limit
Topic.The technological design has solvent refluxing equipment, and solvent utilization rate is high.A kind of efficient, economic, green is provided for bisphenol S synthesis
Technique and device.Meanwhile the hypergravity equipment has the characteristics that low cost, operating flexibility are big, occupied area is small.
Detailed description of the invention
Fig. 1 shows present invention bisphenol synthesis S process flow chart in supergravity reactor, and the number in figure is explained as follows:
In figure: 1- phenol and mesitylene head tank, the 2- concentrated sulfuric acid (sulfonating agent) head tank, 5,6,12,18,23- pump, 7,
8,9,14,15,20,22- valve, 3,4,13,19,21- fluid flowmeter, the first supergravity reactor of 10-, 11- first are stirred
Reactor, the second supergravity reactor of 16-, the second stirred tank reactor of 17-, 24- water diversion system, 25- Liquid liquid Separation system,
26- washing, crystal system, the discharging of 26- bisphenol S, 27 product discharges, the charging of 28- detergent, the discharging of 29- reflux water-dividing.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Phenol and mesitylene dissolve at 65 DEG C, and phosphorous acid is added, and are pumped by pump 5, are controlled and are flowed by flowmeter 3
Amount, is pumped into the first supergravity reactor 10, and the concentrated sulfuric acid is pumped into the first supergravity reactor 10 by pump 6；Sulfonating reaction is opened
Begin, by adjusting the revolving speed of motor, the temperature and flow control reaction temperature of cooling medium, control valve 14,15 in water leg
Carry out control loop amount.By 22 supplement phenol and partial solvent, stirred at the-the second supergravity reactor of sulfone system 16, second
Occur to react at sulfone in kettle reactor 17, water diversion system 24 separates into the water that sulfone reaction generates；It will by Liquid liquid Separation system 25
Mesitylene is separated and is recycled in 1, and material flows into washing, crystal system, and cleaning solution is flowed into from 28, and product is discharged from 27.The
Two sets of hypergravity reaction systems 16,17 are connected with water diversion system 24, react on one side, remove into the water that sulfone reaction generates on one side,
Dewatering time is 2 hours.
The sulfonation system and include supergravity reactor and reaction kettle at sulfone system, the reaction kettle, for reacting,
The material that aging exports out from supergravity reactor.
The hypergravity machine is equipped with rotatable parts in closed shell, is provided with liquid import and export on shell and upper lid
And gas import and export；The rotatable parts are made of rotor and filler；The filler is selected from wire mesh packing, polytetrafluoro is filled out
Material, ceramic packing, structuring filling or structured packing；The liquid-inlet is equipped with the liquid point extended in rotor center cavity
Cloth device.Reaction temperature passes through supergravity reactor and heat medium temperature and flow control in the outer water leg of stirred tank.It obtains thick
15~20% ethanol water washing is added into solvent removal is crossed in product bisphenol S, and crystallisation by cooling obtains product.The method of the present invention
The low product of purity is high, 2,4 ' content of isomer can be obtained, product yield is up to 86%.The raw materials technology is easy to get, process route
Short, the advantage of sintetics excellent performance fully meets industrialization production requirements.
The following are the examples that application apparatus of the present invention carry out bisphenol S.
Embodiment 1:
Hypergravity divides the method for modified starch bisphenol S, and steps are as follows:
1) synthesis of p-hydroxybenzenyl sulfonate
100g mesitylene is taken, phenol 78g is added thereto, 4g phosphorous acid is added as catalysis to 65 DEG C in heating water bath
Raw material is added at one time in head tank by agent, and concentrated sulfuric acid 82g is added in concentrated sulfuric acid head tank, makes n (H2SO4):n(C6H6O)
=1:1, n (C9H12):n(C6H6O)=1:1.It is warming up to 100 DEG C.Agitating paddle, supergravity reactor are opened, hypergravity reaction is adjusted
Device spinner velocity maintains the revolving speed of supergravity reactor 10 in 2000rpm.After temperature and equipment are stablized, start to feed, feed
Speed 250mL/min, charging finish, and recycle 3min, and product enters the second supergravity reactor.
2) synthesis of bisphenol S
Having the p-hydroxybenzenyl sulfonate synthesized in step 1) is that the benzene of step 1) moderate is added at one of sulfone reaction raw materials
Phenol, supplementing solvent mesitylene open agitating paddle, supergravity reactor, cooling for reflux system, maintain 16 turns of supergravity reactor
For speed in 2000rpm, the reflux dewatering time is 1.2h.When temperature reaches 165 DEG C, charging rate 250mL/min, circulation
3min.Material feed liquor liquid separation system by dilution, cooling, crystallizes to obtain bisphenol S crude product.Bisphenol S yield is in crude product
84.5%, the content 88.55% of bisphenol S.
Embodiment 2:
Hypergravity divides the method for modified starch bisphenol S, and steps are as follows:
150g mesitylene is taken, phenol is added thereto, to 65 DEG C 4g phosphorous acid is added as catalyst in heating water bath,
Raw material is added at one time in head tank, the concentrated sulfuric acid is added in concentrated sulfuric acid head tank, makes n (H2SO4):n(C6H6O)=1.1:
1, n (C9H12):n(C6H6O)=1:1.1.100 DEG C are warming up to, agitating paddle, supergravity reactor are opened, adjusts supergravity reactor
Spinner velocity maintains the revolving speed of supergravity reactor 10 in 2000rpm.After temperature and equipment are stablized, start to feed, charging speed
250mL/min is spent, charging finishes, and recycles 3min, and product enters the second supergravity reactor.
2) synthesis of bisphenol S
Having the p-hydroxybenzenyl sulfonate synthesized in step 1) is that the benzene of step 1) moderate is added at one of sulfone reaction raw materials
Phenol, supplementing solvent mesitylene open agitating paddle, supergravity reactor, cooling for reflux system, maintain 16 turns of supergravity reactor
For speed in 2000rpm, the reflux dewatering time is 1.2h.When temperature reaches 165 DEG C, charging rate 250mL/min, circulation
3min.Material feed liquor liquid separation system by dilution, cooling, crystallizes to obtain bisphenol S crude product.Bisphenol S yield is in crude product
85.75%, the content 89.55% of bisphenol S.
Embodiment 3:
Hypergravity divides the method for modified starch bisphenol S, and steps are as follows:
150g mesitylene is taken, phenol is added thereto, to 65 DEG C 4g phosphorous acid is added as catalyst in heating water bath,
Raw material is added at one time in head tank, the concentrated sulfuric acid is added in concentrated sulfuric acid head tank, makes n (H2SO4):n(C6H6O)=1.1:
1, n (C9H12):n(C6H6O)=1:1.1.100 DEG C are warming up to, agitating paddle, supergravity reactor are opened, adjusts supergravity reactor
Spinner velocity maintains the revolving speed of supergravity reactor 10 in 2500rpm.After temperature and equipment are stablized, start to feed, charging speed
300mL/min is spent, charging finishes, and recycles 0min, and product enters the second supergravity reactor.
2) synthesis of bisphenol S
It is that the benzene of step 1) moderate is added at one of sulfone reaction raw materials by the p-hydroxybenzenyl sulfonate synthesized in step 1)
Phenol, supplementing solvent mesitylene open agitating paddle, supergravity reactor, cooling for reflux system, maintain 16 turns of supergravity reactor
For speed in 2500rpm, the reflux dewatering time is 1.2h.When temperature reaches 165 DEG C, charging rate 300mL/min, circulation
3min.Material feed liquor liquid separation system by dilution, cooling, crystallizes to obtain bisphenol S crude product.Bisphenol S yield is in crude product
85.5%, the content 84.77% of bisphenol S.
Embodiment 4:
Hypergravity divides the method for modified starch bisphenol S, and steps are as follows:
100g mesitylene is taken, phenol is added thereto, to 65 DEG C 4g phosphorous acid is added as catalyst in heating water bath,
Raw material is added at one time in head tank, the concentrated sulfuric acid is added in concentrated sulfuric acid head tank, makes n (H2SO4):n(C6H6O)=1.1:
1, n (C9H12):n(C6H6O)=1:1.1.100 DEG C are warming up to, agitating paddle, supergravity reactor are opened, adjusts supergravity reactor
Spinner velocity maintains the revolving speed of supergravity reactor 10 in 2500rpm.After temperature and equipment are stablized, start to feed, charging speed
250mL/min is spent, charging finishes, and recycles 3min, and product enters the second supergravity reactor.
2) synthesis of bisphenol S
It is that the benzene of step 1) moderate is added at one of sulfone reaction raw materials by the p-hydroxybenzenyl sulfonate synthesized in step 1)
Phenol, supplementing solvent mesitylene open agitating paddle, supergravity reactor, cooling for reflux system, maintain 16 turns of supergravity reactor
For speed in 2500rpm, the reflux dewatering time is 1.5h.When temperature reaches 165 DEG C, charging rate 250mL/min, circulation
3min.Material feed liquor liquid separation system by dilution, cooling, crystallizes to obtain bisphenol S crude product.Bisphenol S yield is in crude product
89.52%, the content 86.23% of bisphenol S.
Embodiment 5:
Hypergravity divides the method for modified starch bisphenol S, and steps are as follows:
100g mesitylene is taken, phenol is added thereto, to 65 DEG C 4g phosphorous acid is added as catalyst in heating water bath,
Raw material is added at one time in head tank, the concentrated sulfuric acid is added in concentrated sulfuric acid head tank, makes n (H2SO4):n(C6H6O)=1.1:
1, n (C9H12):n(C6H6O)=1:1.1.100 DEG C are warming up to, agitating paddle, supergravity reactor are opened, adjusts supergravity reactor
Spinner velocity maintains the revolving speed of supergravity reactor 10 in 2000rpm.After temperature and equipment are stablized, start to feed, charging speed
300mL/min is spent, charging finishes, and recycles 3min, and product enters the second supergravity reactor.
2) synthesis of bisphenol S
It is that the benzene of step 1) moderate is added at one of sulfone reaction raw materials by the p-hydroxybenzenyl sulfonate synthesized in step 1)
Phenol, supplementing solvent mesitylene open agitating paddle, supergravity reactor, cooling for reflux system, maintain 16 turns of supergravity reactor
For speed in 2000rpm, the reflux dewatering time is 2h.When temperature reaches 165 DEG C, charging rate 300mL/min recycles 3min.
Material feed liquor liquid separation system by dilution, cooling, crystallizes to obtain bisphenol S crude product.Bisphenol S yield is 84.23% in crude product, double
The content 87.56% of phenol S.
Embodiment 6:
Hypergravity divides the method for modified starch bisphenol S, and steps are as follows:
150g mesitylene is taken, phenol is added thereto, to 65 DEG C 4g phosphorous acid is added as catalyst in heating water bath,
Raw material is added at one time in head tank, the concentrated sulfuric acid is added in concentrated sulfuric acid head tank, makes n (H2SO4):n(C6H6O)=1.2:
1, n (C9H12):n(C6H6O)=1:1.2.100 DEG C are warming up to, agitating paddle, supergravity reactor are opened, adjusts supergravity reactor
Spinner velocity maintains the revolving speed of supergravity reactor 10 in 2500rpm.After temperature and equipment are stablized, start to feed, charging speed
250mL/min is spent, charging finishes, and recycles 3min, and product enters the second supergravity reactor.
2) synthesis of bisphenol S
It is that the benzene of step 1) moderate is added at one of sulfone reaction raw materials by the p-hydroxybenzenyl sulfonate synthesized in step 1)
Phenol, supplementing solvent mesitylene open agitating paddle, supergravity reactor, cooling for reflux system, maintain 16 turns of supergravity reactor
For speed in 2500rpm, the reflux dewatering time is 2h.When temperature reaches 165 DEG C, charging rate 250mL/min recycles 3min.
Material feed liquor liquid separation system by dilution, cooling, crystallizes to obtain bisphenol S crude product.Bisphenol S yield is 84.21% in crude product, double
The content 87.33% of phenol S.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (6)
1. a kind of hypergravity prepares the device of bisphenol S, including hypergravity sulfonating reaction system, hypergravity into sulfone reaction system, liquid
Liquid separation system is condensed back system, crystal system；Phenol is overweight by valve, pump and first with mesitylene feed pot (1)
The connection of power reactor (10) feed inlet, concentrated sulfuric acid feed pot (2) pass through valve, pump and the first supergravity reactor (10) feed inlet
Connection；First supergravity reactor (10) liquid outlet is connect with the first stirred reactor (11), and the first stirred reactor (11) is logical
Cross valve, pump is connect with the first supergravity reactor (10) feed inlet, formation hypergravity sulfonating reaction circulation loop；First stirring
Reactor (11) is connect by valve, pump with the feed inlet of the second supergravity reactor (16), the second supergravity reactor (16)
Feed inlet also pass through valve, pump and concentrated sulfuric acid feed pot (2) connect, the liquid outlet and second of the second supergravity reactor (16)
Stirred reactor (17) connection, the charging that the second stirred reactor (17) passes through pump, valve and the second supergravity reactor (16)
Mouth connection forms hypergravity into sulfone reaction cycle circuit；Second supergravity reactor (16) is additionally provided with gas vent, gas vent
It is connect with water diversion system (24), water diversion system (24) can separate the water that reaction generates；Second stirred reactor (17) passes through pump, valve
Door is connect with Liquid liquid Separation system (25) feed inlet, the discharge port and washing and crystal system of Liquid liquid Separation system (25)
(26) it connects, another discharge port of Liquid liquid Separation system (25) is connect with phenol with mesitylene feed pot (1).
2. the method for preparing bisphenol S using device described in claim 1, which is characterized in that phenol and mesitylene are heating
Under the conditions of dissolve, phosphorous acid is added, is pumped into the first supergravity reactor by pump, centre by flowmeter controls flow；Together
When the concentrated sulfuric acid be pumped into the first supergravity reactor (10) by pump；Sulfonating reaction starts, by adjusting supergravity reactor electricity
The flow of the temperature of cooling medium and reactive material controls reaction temperature in the revolving speed of machine, supergravity reactor water leg, adjusts
Section valve carrys out internal circulating load in adults power sulfonating reaction circulation loop, and sulfonating reaction is carried out in this cyclic process；By
Solution in one stirred reactor (11) is pumped into the second supergravity reactor, by constantly supplementing into the second supergravity reactor
Phenol and partial solvent divide water system at occurring to react at sulfone in the second supergravity reactor of sulfone system, the second stirred reactor
System (24) separates into the water that sulfone reaction generates；Mesitylene is removed by Liquid liquid Separation system (25) and is recycled to phenol and equal three
In toluene feed pot (1), product material flows into washing, crystal system (26) is washed, crystallized.
3. according to method for claim 2, which is characterized in that
1) intermediate-p-hydroxybenzenyl sulfonate synthesis:
Phenol is added in mesitylene, and temperature control is added phosphorous acid, is pumped into the first supergravity reactor, the concentrated sulfuric acid at 65 DEG C
It is pumped into the first supergravity reactor, constant 100 DEG C of temperature, circular response 25min, aging 30min；
2) synthesis of bisphenol S:
The phenol of synthesis moderate with p-hydroxybenzenyl sulfonate is pumped into the second supergravity reactor, is situated between by heat in water leg
Matter regulation is 165 DEG C at sulfone temperature, opens water diversion system, circular response 2 hours, liquid separation removed water, and mesitylene is simultaneously back to
Second supergravity reactor, the product that Liquid liquid Separation system (25) is isolated obtain bisphenol S through cooling, washing, crystallization.
4. according to the method for right 3, which is characterized in that the molar ratio of phenol and mesitylene is (0.8-1.5) in step 1): 1,
The molar ratio of the concentrated sulfuric acid and phenol is (1-1.5): 1,4g phosphorous acid is added in every 100g-150g mesitylene.
5. according to method for claim 2, which is characterized in that the rotatable parts of supergravity reactor are made of rotor and filler；
The filler is selected from wire mesh packing, polytetrafluoro filler, ceramic packing, structuring filling or structured packing；Liquid-inlet is set
There is the liquid distribution trough extended in rotor center cavity.
6. according to method for claim 2, which is characterized in that obtain crude product bisphenol S by Liquid liquid Separation solvent removal, be added 15
~20% ethanol water washing, crystallisation by cooling obtain product.
Priority Applications (1)
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