CN105085192B - Method for producing high-purity bisphenol F - Google Patents
Method for producing high-purity bisphenol F Download PDFInfo
- Publication number
- CN105085192B CN105085192B CN201510192485.3A CN201510192485A CN105085192B CN 105085192 B CN105085192 B CN 105085192B CN 201510192485 A CN201510192485 A CN 201510192485A CN 105085192 B CN105085192 B CN 105085192B
- Authority
- CN
- China
- Prior art keywords
- evaporator
- bisphenol
- thin film
- evaporimeter
- film evaporator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920003986 novolac Polymers 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 29
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 28
- 229930185605 Bisphenol Natural products 0.000 claims description 28
- 238000004821 distillation Methods 0.000 claims description 25
- 230000008020 evaporation Effects 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001577 simple distillation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- -1 phenol compound Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
- B01D1/222—In rotating vessels; vessels with movable parts
- B01D1/223—In rotating vessels; vessels with movable parts containing a rotor
- B01D1/227—In rotating vessels; vessels with movable parts containing a rotor with brushes
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
- C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for producing high-purity bisphenol F. Rough bisphenol F and/or rough novolac resin are separated via a distilling procedure to achieve distilling components and high-purity bisphenol F can be acquired. The method for producing high-purity bisphenol F is characterized in that a vertical rotary thin film evaporator is employed; during the distilling procedure, the evaporator is provided with a heating mechanism; the upper part of the evaporator is equipped with a liquid supplying port and a steam discharging port; the lower part of the evaporator is provided with a residual discharging port; a main body part of the evaporator is equipped with a cylindrical evaporator body and a winged internal rotation body; the internal rotation body is disposed in the body and circumferentially moves in the inner wall surface of the evaporator body; the winged internal rotation body is provided with a windshield wiper-shaped component having a groove and having a direct contact with a heating evaporating surface of the internal periphery of the body; the winged internal rotation body is further provided with steam path space; and a condenser is arranged outside the thin film evaporator.
Description
Technical field
The present invention relates to a kind of manufacture method of high-purity bisphenols F, it can be efficiently obtained by high-purity by distillation
Bisphenol F.
Background technology
In general, general Bisphenol F is the Bisphenol F containing 85～93 weight % dicaryons, preferably containing 90～93 weights
Amount % or so, for as the raw material of low viscosity epoxy resin.With regard to general Bisphenol F, by the way that phenol is rubbed with the reaction of formaldehyde
You are set to 20～50 than (P/F), so as to obtain the Bisphenol F useful as the raw material of epoxy resin.In this regard, high-purity bisphenols F
It is the Bisphenol F that there are more dicaryons than general Bisphenol F, for as the raw material of coating epoxy resin.For example, with by containing
The epoxy resin that the Bisphenol F of the dicaryon of 92 weight % is obtained is compared as the coating of constituent, will be by containing 95 weight %
More than dicaryon the epoxy resin that obtains of Bisphenol F as constituent corrosion resistance, chemicals-resistant of the coating in film
The aspects such as property are excellent.In addition, by bifunctional epoxy resin and bivalent phenol compound manufacture HMW bifunctional epoxy resin
Method in, the dicaryon purity of bivalent phenol compound is necessary for more than 95 weight %, if in the case of below the purity,
Will be unable to obtain to produce insoluble (gelation) as purpose epoxy resin when HMW body is manufactured.With regard to by phenol with
The reaction of formaldehyde and to obtain the content of dicaryon be high-purity bisphenols F more than 98 weight %, even if reaction mol ratio P/F is set
Cannot also reach for more than 100, be industrially impossible.Then, as the method for manufacture high-purity bisphenols F, it is proposed that
Following method, wherein, high-purity bisphenols F is obtained or to the mixing based on dicaryon by more than two sections of multistage distillation
Thing is recrystallized and is obtained high-purity bisphenols F.In addition, it is also proposed the evaporation that multistage distillation structure is set to inside evaporimeter
Device (patent document 1).Also, make in the manufacture method as the high-purity bisphenols F that high-purity bisphenols F is obtained by distillation
Distilling apparatus, the example (patent document 2) of not special provision.
Prior art literature
Patent document
Patent document 1：JP Laid-Open 3-238001 publication
Patent document 1：JP Laid-Open 6-128183 publication
The content of the invention
The invention problem to be solved
The present invention provides the manufacturer that can obtain the stable high-purity bisphenols F of proterties with high yield rate in simple distillation
Method and the vertical rotating formula thin film evaporator of high-purity bisphenols F manufactures.
For solving the technical scheme of problem
The present inventor in order to by by thick Bisphenol F, thick novolac resin as dicaryon composition Distillation recovery with height
Yield rate obtains high-purity bisphenols F, it is stipulated that most efficient distilling apparatus, and it was found that its distillation condition, thus, it was found that
The manufacture method of high-purity bisphenols F little to carrying capacity of environment and being conducive to cost reduction, so as to complete the present invention.
That is, in the manufacture method of the high-purity bisphenols F of the present invention, by distillation process by thick Bisphenol F and/or crude phenols
Novolac resin is separated, and as distillation composition high-purity bisphenols F is obtained, wherein, the thick Bisphenol F and/or crude phenols Novolac tree
Fat is reacted by making phenol and formaldehyde in the presence of a catalyst, acid catalyst, water are removed from the product for being obtained with
And unreacted phenol and obtain, it is characterised in that used vertical rotating formula thin film evaporator, the vertical rotating formula film steams
In sending out device, there are heating arrangements, top there is liquid supply mouth and steam to discharge for the outside of the evaporimeter used in distillation process
Mouth, bottom have sludge discharge tube, and the main part of the evaporimeter has the evaporator body of cylindrical shape and the inside with the wing
Rotary body, the inner rotary body be arranged at body interior and along evaporator body internal face and in circumferential movement, wherein, carry
The inner rotary body of the wing has and the slotted rain brush shape of band of the heating evaporation face directly contact of the inner peripheral surface of body device metastomium
Part, and in addition to supporting the part of the part with slotted rain brush shape, the also space with vapor passageway, condensation
Device is arranged at the outside of thin film evaporator.
In above-mentioned distillation process, preferably in the evaporimeter for keeping 1～10mmHg of pressure, 250～320 DEG C of heat medium temperature
In, according to the heat-conducting area of the evaporimeter per 1m2For the mode of the quantity delivered of 30～200Kg/h, continuously supply the thick Bisphenol F or
The thick novolac resin, while evaporation composition and bottom of towe composition are continuously withdrawn from the evaporimeter, while it is double to obtain high-purity
Phenol F.
In addition, above-mentioned manufacture method obtain be according to gel permeation chromatography (GPC) determine dicaryon content be 95 faces
The high-purity bisphenols F of product more than %.
Also, with regard to the vertical rotating formula thin film evaporator used in above-mentioned manufacture method, wherein, make in distillation process
There are heating arrangements, top there is liquid supply mouth and steam outlet, bottom to have sludge discharge tube for the outside of evaporimeter,
The main part of the evaporimeter has the evaporator body and the inner rotary body with the wing of cylindrical shape, and the inner rotary body sets
Be placed in body interior and along evaporator body internal face and in circumferential movement, wherein, the inner rotary body with the wing have with
The part of the slotted rain brush shape of band of the heating evaporation face directly contact of the inner peripheral surface of body device metastomium, and except supporting the band
Beyond the part of the part of slotted rain brush shape, the also space with vapor passageway, condenser is arranged at thin film evaporator
It is outside.
The effect of invention
The manufacture method of the present invention can obtain high-purity bisphenols F with high yield rate, and generally, it is negative to environment
Lotus is little, favourable in terms of cost reduction.
Description of the drawings
Fig. 1 is the longitudinal section ideograph of an example of the thin film evaporator of the present invention；
Fig. 2 is the longitudinal section ideograph of another example of the thin film evaporator of the present invention；
Fig. 3 is the ideograph of the example of the rain brush body of the inner rotary body with the wing for being installed on Fig. 1；
Fig. 4 is the ideograph of the example of the rain brush body of the inner rotary body with the wing for being installed on Fig. 2.
Specific embodiment
Embodiments of the present invention are described in detail below.
It is more than 95 weight % preferably 98 weights as the dicaryon of formula (1) with regard to the high-purity bisphenols F of the present invention
Amount more than %, more than more preferably 99 weight %.In addition, being supplied in the thick Bisphenol F of distillation, general Bisphenol F substantially by formula
(1) as principal component, the formula containing 7～15 weight % (2) reduces raw material phenol, catalysts or reaction secondary as impurity
Product is until almost negligible degree.
[changing 1]
[changing 2]
Therefore, the process that high purity Bisphenol F is obtained by distillation is simply that formula (2) is separated from general Bisphenol F
Three nucleome compositions behavior.The steam of formula (1) and formula (2) is pressed with very big difference, will not azeotropic, even if therefore entering
The so-called simple distillation of row also can be separated sufficiently.But, there is separating power more than necessity in existing distiller.
In addition, the distillation under seeking low temperature, needs the low vacuum condition more than necessary.
In addition, in vertical rotating formula thin film evaporator also have various types, such as condenser internally or
It is arranged on the type of outside, agitator to have more than rain brush body or the not type with rain brush body, the voidage in internal rotating portion
Type that type, agitator are obliquely installed etc..
In the present invention, it is thin with the vertical rotating formula for being isolated high-purity bisphenols F of necessity and sufficiency by simple distillation
Film evaporator is the type that condenser is arranged at outside, and the type of rain brush body is provided with agitator, inner rotary body
Voidage is high.
In the present invention, external condenser is necessary condition.If internal condensation device type, even if equipped with mist point
From device, general Bisphenol F, thick Bisphenol F or the thick novolac resin (hereinafter referred to as supplying liquid) of distillation process are supplied in distillation
With the substantial amounts of spittle in composition, as a result cannot make to be distilled into be divided into high-purity bisphenols F.Although can also descend certain time pair
Distillation condition is improved so as to reduce with the amount of the spittle, but in this occasion, is supplied in the supply of the supply liquid of evaporimeter
Speed can extremely be slowed down, and productivity can deteriorate, and become the main cause for causing integrated cost to rise.
In addition, in external condenser type, although also there is setting point contracting to compare, the type more subtly distilled,
But not no necessity in the distillation of Bisphenol F, generally superfluous quality, can cause cost increase.
In addition, it is required, the preferably rain brush body of trough of belt that inner rotary body has rain brush body.Although the installation of rain brush body
Mode arbitrarily, but needs to make rain brush body be close contact on the internal face of cylinder, therefore compared to fixed rain brush body, more preferably carries
The movable type of spring or the movable type for passing through centrifugal force.The occasion of fixed rain brush body, needs the internal face of cylinder
Below 1mm is set to the interval of rain brush body, but if if rain brush body is grounded with the internal face of cylinder, rain brush body can be cut down, because
And it is preferred.In addition, the rain brush body of trough of belt can quickly make supply liquid filming, and uniform heating part, thus it is preferred that.
In addition, as the material of rain brush body, preferably not damaging material as the internal face of thin film evaporator, more preferably
Even if in resin, metal vacuum impregnating by pressure in carbon at a high temperature of improve mechanical strength, the mixing carbon that could be used that or corrosion
Strong fluororesin etc., more preferred long-time shape stability is excellent, even if the mixing carbon that could be used that at high temperature.
Furthermore it is possible to the type that rotary wings are installed in rotary shaft for inner rotary body, or columnar skeleton class
Type, but voidage when inner rotary body to be regarded as cylinder is preferably more than 70 capacity %, more preferably more than 85 capacity %.It is interior
The voidage of portion's rotary body is bigger, then the outflow for distilling composition is easier, thus it is preferred that.On the other hand, inside is also easily caused
The intensity decreases of rotary body, consider from both balances, and preferred voidage is 85 capacity % or so.
In addition, the top of inner rotary body is the path for evaporating composition towards evaporation composition outlet, therefore in order that the outflow
Become easy, the intensity of preferred holding necessity and sufficiency, and the hole with path, or it is made clathrate.
Fig. 1,3 are the example of the rotary body 3 that four agitators 6 are mounted with rotary shaft 5, and it is of following structure
Example：Whole ends of the agitator or a part are provided with rain brush body 11, and the inwall of heating chuck 1 makes rain by spring
Brush body touches.The piece number of agitator need not be four, arbitrarily be 3～12 also dependent on size.In addition, rain brush body sets
Put also without the overall end face in agitator.Fig. 2,4 to connect the columnar rotation of upper lower disc by four pillars
The example of body, the radical of pillar need not be four, arbitrarily be 3～24 also dependent on size.Pillar is used not only for connecting
Connect down, also for setting rain brush body.The example is an example of following structure：In the inside of the pillar of trough of belt, rain brush is set
Body, makes rain brush body be close contact in the inwall of heating chuck by centrifugal force.Touching hypodynamic occasion etc., it is possible to use bullet
Spring etc. and carry out enforceable contiguity.In addition, in order that top is the path for evaporating composition, making bottom eliminate supply liquid and depositing
Stay, therefore need to be provided with hole as shown in Figure 4.Also, can be disk with holes if intensity, clathrate can be also processed as.
Although Fig. 1～2 show the longitudinal section ideograph of an example of the vertical rotating formula thin film evaporator of the present invention,
But as long as the present invention is just not limited only to the example without departing from the main idea.This device is possess outside with heating chuck 1
The thin film evaporator of columnar main part 2, with inner rotary body 3, make its rotate motor 4.Inner rotary body can be
The type of agitator 6 is installed in rotary shaft 5.The rain brush body 11 for being installed on inner rotary body connects with the wall of main part and revolves
Turn.The liquid to be treated supplied from the liquid supply mouth 7 on thin film evaporator top is by the rain brush body that rotates along the inwall of main part
While launch in membranaceous pressing, while being flowed down according to gravity.During this is flowed down, by coming from heating chuck
Heat, supplies above-mentioned formula (1) the composition evaporation in liquid.Vaporized formula (1) composition is from positioned at the top of thin film evaporator
Evaporation composition outlet 8 and be exported to outside system, evaporate composition major part be removed, mobility be deteriorated evaporation residue
Tower bottom 9 is directed to, is discharged from the sludge discharge tube 10 positioned at the bottom of thin film evaporator.Formula (1) composition is in stream
Evaporate during lower, therefore the voidage of inner rotary body is critically important, is set as not affecting the structure evaporated to be critically important.
In addition, the set location of external condenser be preferably vapor outlet port it is few and away from region.If from vapor outlet port
If near, then easily can be affected with the spittle by supplying liquid as internal condensation device, it is not preferable.In design, outward
Portion's condenser is arranged under the occasion near vapor outlet port, must need to arrange mist separator therebetween.In order to prevent companion
There is the spittle to occur, the setting area of preferred external condenser is twice of evaporimeter length or so, is preferably connected with external condenser
The tube diameter for connecing is 1/2～3/5 of Jing in evaporimeter.
As the distillation condition for obtaining high-purity bisphenols F of the present invention, preferably 1～10mmHg of pressure, heating agent temperature are being kept
In the evaporimeter of 250～320 DEG C of degree, according to the heat-conducting area of the evaporimeter per 1m2For the side of the quantity delivered of 30～200Kg/h
Formula, continuous supply supply liquid.
The pressure of distillation condition is more preferably 3～8mmHg, is still more preferably 4～7mmHg, most preferably 5～
6mmHg.In the low occasion of pressure, if heat medium temperature is very high, evaporation capacity can become many, and the thing followed supplies liquid with the spittle
Situation can become many, not preferably.If reducing heat medium temperature according to evaporation capacity, with the occasion that heat medium temperature is high, pressure is high
Compare, reduce as the evaporation capacity of the above-mentioned formula (1) of purpose thing, it is not preferable.
Heat medium temperature is more preferably 260～300 DEG C, is still more preferably 270～290 DEG C.The occasion of low temperature, particularly
Less than 250 DEG C, if significantly pressure is not reduced evaporation capacity is unable to maintain that, and the occasion also can increase with fly
Foam amount increases, and as a result possibly cannot obtain high-purity bisphenols F.In addition, if for if high temperature, can produce supply liquid decomposition,
Coloring, the physical property that may make the high-purity bisphenols F as purpose thing is deteriorated.
The supply liquid measure for being supplied in evaporimeter is more preferably the heat-conducting area of evaporimeter per 1m2For 30～150Kg/h, enter
One step is preferably 50～120kg/h, most preferably 70～100kg/h.If quantity delivered is more, then as the above-mentioned of purpose thing
Formula (1) separate with supply liquid it is insufficient, possibly cannot obtain high-purity bisphenols F.
[embodiment]
Hereinafter, the present invention is specifically described based on embodiment, but the present invention is not limited only to this.In embodiment,
If not otherwise specified, " part " represents mass parts, and " % " represents quality %.Also, double in embodiment and comparative example
The purity testing of nucleome is implemented by following methods.
Dicaryon purity：Obtain the area % of GPC measure.The condition determination of GPC is as follows.
Chromatographic column:G4000HXL+G2500HXL+G2000HXLX 2 (Tosoh Corporation systems)
Chromatogram column temperature：40 degree
Eluent:Tetrahydrofuran
Flow velocity：1mL/min
Sample concentration：0.1g/10mL tetrahydrofurans
Detector：RI is detected
Embodiment 1
Using thin film evaporator (the heat transfer face 0.21m of the present invention2, external condenser conducting surface 1.3m2, with only spring
The rain brush body of fluororesin), 280 DEG C of heating agent is flow through in heating jacket, 120 DEG C of heating is flow through in external condenser
Water, by rotor revolution number 250rpm is set to, with 21kg/h companies in the thin film evaporator of the state operated under 5～6mmHg of vacuum
Continuous supply 1 hour, it is continuous to discharge evaporation composition and bottom of towe composition, respectively obtain Bisphenol F and novolac resin.
Embodiment 2
Using thin film evaporator (the heat transfer face 0.21m of the present invention2, external condenser conducting surface 1.3m2, with only spring
The rain brush body of fluororesin), 260 DEG C of heating agent is flow through in heating jacket, 120 DEG C of heating is flow through in external condenser
Water, by rotor revolution number 250rpm is set to, continuous with 8kg/h in the thin film evaporator of the state operated under 3～4mmHg of vacuum
Supply 1 hour, it is continuous to discharge evaporation composition and bottom of towe composition, respectively obtain Bisphenol F and novolac resin.
Embodiment 3
Using thin film evaporator (the heat transfer face 0.21m of the present invention2, external condenser conducting surface 1.3m2, with only spring
The rain brush body of fluororesin), 300 DEG C of heating agent is flow through in heating jacket, 120 DEG C of heating is flow through in external condenser
Water, by rotor revolution number 250rpm is set to, with 30kg/h companies in the thin film evaporator of the state operated under 6～7mmHg of vacuum
Continuous supply 1 hour, it is continuous to discharge evaporation composition and bottom of towe composition, respectively obtain Bisphenol F and novolac resin.
Comparative example 1
Using thin film evaporator (the heat transfer face 0.40m different from the present invention2, internal condensation device conducting surface 1.3m2, band
Have the rain brush body of only spring fluororesin), 280 DEG C of heating agent is flow through in heating jacket, 120 DEG C are flow through in external condenser
Plus hot water, rotor revolution number is set to into 250rpm, with 40kg/ in the thin film evaporator of the state operated under 5～6mmHg of vacuum
H is continuously supplied 1 hour, continuous to discharge evaporation composition and bottom of towe composition, respectively obtains Bisphenol F and novolac resin.
Comparative example 2
Using thin film evaporator (the heat transfer face 0.30m different from the present invention2, external condenser conducting surface 1.3m2, nothing
The gap 1.5mm of rain brush body, main part and inner rotary body), 280 DEG C of heating agent is flow through in heating jacket, in external condensation
Flow through in device 120 DEG C plus hot water, rotor revolution number is set to into 1470rpm, under 5～6mmHg of vacuum operate state it is thin
Continuously supplied 1 hour with 30kg/h in film evaporator, it is continuous to discharge evaporation composition and bottom of towe composition, respectively obtain Bisphenol F and phenol
Novolac resin.
The dicaryon purity of the Bisphenol F obtained by embodiment 1～3 and comparative example 1,2 is shown in table 1.
[table 1]
In the thin film evaporator of the present invention, i.e., along the internal face for being arranged at its internal evaporator body in circumferential movement
The inner rotary body with the wing vertical rotating formula thin film evaporator in, the inner rotary body with the wing have and body device trunk
The part of the slotted rain brush shape of band of the heating evaporation face directly contact of the inner peripheral surface in portion, and except supporting this with slotted rain
Space with vapor passageway beyond the part of the part of brush, condenser is arranged at the outside of thin film evaporator, if
If above-mentioned thin film evaporator, even if changing distillation condition, it is also possible to obtain high-purity bisphenols F by simple distillation.With its phase
Right, in having used the comparative example of the thin film evaporators different from the present invention, dicaryon purity is relatively low, it is impossible to obtain high-purity bisphenols
F。
The explanation of label：
Label 1 represents heating chuck；
Label 2 represents main part；
Label 3 represents inner rotary body；
Label 4 represents motor；
Label 5 represents rotary shaft；
Label 6 represents agitator；
Label 7 represents liquid supply mouth；
Label 8 represents evaporation composition outlet；
Label 9 represents tower bottom；
Label 10 represents sludge discharge tube；
Label 11 represents rain brush body；
Label 12 represents rain brush body installation portion；
Label 13 represents spring.
Claims (3)
1. a kind of manufacture method of Bisphenol F, is separated thick Bisphenol F and/or thick novolac resin by distillation process, as
Distill composition and obtain high-purity bisphenols F, wherein, the thick Bisphenol F and/or thick novolac resin are by the presence in catalyst
Under react phenol and formaldehyde, remove acid catalyst, water and unreacted phenol from the product for being obtained and obtain,
Characterized in that, having used vertical rotating formula thin film evaporator, in the vertical rotating formula thin film evaporator, make in distillation process
There are heating arrangements, top there is liquid supply mouth and steam outlet, bottom to have sludge discharge tube for the outside of evaporimeter,
The main part of the evaporimeter has the evaporator body and the inner rotary body with the wing of cylindrical shape, and the inner rotary body sets
Be placed in body interior and along evaporator body internal face and in circumferential movement, wherein, the inner rotary body with the wing have with
The part of the slotted rain brush shape of band of the heating evaporation face directly contact of the inner peripheral surface of body device metastomium, and except supporting the band
Beyond the part of the part of slotted rain brush shape, the also space with vapor passageway, condenser is arranged at thin film evaporator
It is outside.
2. the manufacture method of Bisphenol F according to claim 1, wherein, in above-mentioned distillation process, keep pressure 1～
In 10mmHg, the evaporimeter of 250～320 DEG C of heat medium temperature, according to the heat-conducting area of the evaporimeter per 1m2For 30～200Kg/h
Quantity delivered mode, the thick Bisphenol F or the thick novolac resin are continuously supplied, while being continuously withdrawn steaming from the evaporimeter
Composition and bottom of towe composition are sent out, while obtaining high-purity bisphenols F.
3. the vertical rotating formula thin film evaporator of a kind of Bisphenol F manufacture, it is used for the manufacture method described in claim 1 or 2
In, wherein, there are heating arrangements, top there is liquid supply mouth and steam to discharge for the outside of the evaporimeter used in distillation process
Mouth, bottom have sludge discharge tube, and the main part of the evaporimeter has the evaporator body of cylindrical shape and the inside with the wing
Rotary body, the inner rotary body be arranged at body interior and along evaporator body internal face and in circumferential movement, wherein, carry
The inner rotary body of the wing has and the slotted rain brush shape of band of the heating evaporation face directly contact of the inner peripheral surface of body device metastomium
Part, and in addition to supporting the part of the part with slotted rain brush shape, the also space with vapor passageway, condensation
Device is arranged at the outside of thin film evaporator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-095858 | 2014-05-07 | ||
| JP2014095858A JP6244259B2 (en) | 2014-05-07 | 2014-05-07 | Method for producing high purity bisphenol F |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105085192A CN105085192A (en) | 2015-11-25 |
| CN105085192B true CN105085192B (en) | 2017-05-10 |
Family
ID=54566629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510192485.3A Active CN105085192B (en) | 2014-05-07 | 2015-04-22 | Method for producing high-purity bisphenol F |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6244259B2 (en) |
| KR (1) | KR101633630B1 (en) |
| CN (1) | CN105085192B (en) |
| TW (1) | TWI576332B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6922575B2 (en) * | 2016-09-14 | 2021-08-18 | 三菱ケミカル株式会社 | Multivalent phenol compound and its manufacturing method |
| CN110841318A (en) * | 2019-12-16 | 2020-02-28 | 江苏怡达化学股份有限公司 | Solidification separation method and separation system for alcohol ether residual liquid |
| CN115581934B (en) * | 2022-10-08 | 2023-06-16 | 山东信谊制药有限公司 | Separation and purification device for drug synthesis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075723A (en) * | 1992-02-27 | 1993-09-01 | 三井东压化学株式会社 | The method for preparing Bisphenol F and novolak phenol resins simultaneously |
| CA2441729A1 (en) * | 2003-09-19 | 2005-03-19 | Labatt Brewing Company Limited | Thin film process for wort production |
| CN1874830A (en) * | 2003-10-02 | 2006-12-06 | Vtu－工程规划及指导有限公司 | Thin-film evaporator |
| CN202105449U (en) * | 2011-04-20 | 2012-01-11 | 蒋树会 | Multi-layer film evaporator and removal system thereof |
| CN102814051A (en) * | 2011-06-09 | 2012-12-12 | 上海恩氟佳科技有限公司 | Polycarbonate-grade bisphenol A refining equipment |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400554A (en) * | 1982-03-29 | 1983-08-23 | Monsanto Company | Process for making bis(hydroxyphenyl)methanes |
| JPH03238001A (en) * | 1990-02-14 | 1991-10-23 | Shinko Pantec Co Ltd | Membrane rectifying tower |
| JPH06128183A (en) * | 1992-02-27 | 1994-05-10 | Mitsui Toatsu Chem Inc | Method for simultaneous production of bisphenol f and novolak type phenolic resin |
| TW215097B (en) * | 1992-02-27 | 1993-10-21 | Mitsui Toatsu Chemicals | |
| JP3294316B2 (en) * | 1992-04-20 | 2002-06-24 | 新日鐵化学株式会社 | Method for producing bisphenol A |
| JP4143218B2 (en) * | 1999-04-23 | 2008-09-03 | 株式会社日本触媒 | Method for preventing polymerization in thin film evaporator and thin film evaporator |
| JP5326966B2 (en) * | 2009-09-25 | 2013-10-30 | Ｄｉｃ株式会社 | Co-production method of bisphenol F and novolac type phenol resin |
| JP5496716B2 (en) * | 2010-03-11 | 2014-05-21 | 新日鉄住金化学株式会社 | Epoxy resin composition for powder coating and cured product thereof |
| CN102516035B (en) * | 2011-12-19 | 2014-04-09 | 胶州市精细化工有限公司 | Preparation method of bisphenol F |
| JP2014018708A (en) * | 2012-07-13 | 2014-02-03 | Osaka Organic Chem Ind Ltd | Vertical type thin film system distiller and wiper for vertical type thin film system distiller |
-
2014
- 2014-05-07 JP JP2014095858A patent/JP6244259B2/en active Active
- 2014-12-22 KR KR1020140186211A patent/KR101633630B1/en active IP Right Grant
-
2015
- 2015-04-22 CN CN201510192485.3A patent/CN105085192B/en active Active
- 2015-04-24 TW TW104113175A patent/TWI576332B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075723A (en) * | 1992-02-27 | 1993-09-01 | 三井东压化学株式会社 | The method for preparing Bisphenol F and novolak phenol resins simultaneously |
| CA2441729A1 (en) * | 2003-09-19 | 2005-03-19 | Labatt Brewing Company Limited | Thin film process for wort production |
| CN1874830A (en) * | 2003-10-02 | 2006-12-06 | Vtu－工程规划及指导有限公司 | Thin-film evaporator |
| CN202105449U (en) * | 2011-04-20 | 2012-01-11 | 蒋树会 | Multi-layer film evaporator and removal system thereof |
| CN102814051A (en) * | 2011-06-09 | 2012-12-12 | 上海恩氟佳科技有限公司 | Polycarbonate-grade bisphenol A refining equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI576332B (en) | 2017-04-01 |
| KR101633630B1 (en) | 2016-06-27 |
| JP2015212245A (en) | 2015-11-26 |
| JP6244259B2 (en) | 2017-12-06 |
| TW201542509A (en) | 2015-11-16 |
| CN105085192A (en) | 2015-11-25 |
| KR20150127527A (en) | 2015-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105085192B (en) | Method for producing high-purity bisphenol F | |
| CA2540707C (en) | Thin-film evaporator | |
| CN101745245B (en) | Multi-level countercurrent rotating bed reaction and rectification device and application thereof | |
| CN100537507C (en) | Method and apparatus for purifying vitamin A intermediate mynistic aldehyde | |
| CN101555243B (en) | Manufacturing method and device of cyclic refined lactic acid dimmer and manufacturing method and device of polylactic acid | |
| CN101848906A (en) | Apparatus and method both relating to polymer synthesis | |
| TW201841882A (en) | Method for distilling dimethyl sulfoxide and multistage distillation tower with which the purification cost is low and dimethyl sulfoxide can be economically purified by distillation | |
| KR101888349B1 (en) | Gas-liquid device | |
| KR101413674B1 (en) | A circle thin film vaporization equipment | |
| CN205182209U (en) | Low temperature evaporation plant of centrifugation of multilayer disk type and gravity film forming and differential decompression | |
| CN101959871A (en) | Be used to prepare and the method and apparatus of purification Epicholorohydrin | |
| CN107098854B (en) | Ethoxyquinoline continuous production method | |
| CN116328685A (en) | System and process method for preparing tetraalkoxysilane by silicon powder direct method | |
| CN205287652U (en) | Horizontal scraper blade concentrator of frequency conversion | |
| CN204932896U (en) | Novel monotubular formula thin film evaporator | |
| CN1454917A (en) | Method of removing volatile component from high-viscosity liquid using rotary packed bed | |
| CN103111252B (en) | Reaction kettle capable of solving reflux wall adhesion problem | |
| CN102600627A (en) | Cyclone-flash cloth-film-reboiling-type heat-pipe distiller | |
| CN205516563U (en) | Wiped film evaporator | |
| CN208770880U (en) | A kind of biomolecule distilling apparatus | |
| JP5418866B2 (en) | Thermal decomposition apparatus and thermal decomposition method | |
| CN209548742U (en) | Molecular distillation apparatus is used in a kind of purification of polyamine | |
| CN106943763B (en) | A kind of rectifier unit suitable for coal-ethylene glycol production waste liquid commercial recovery system | |
| CN107759569A (en) | A kind of synthesis technique and device for improving nicosulfuron purity | |
| CN201855579U (en) | Distilling system for coupling agent KH560 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Han Guoshouer Co-patentee after: NIPPON STEEL & SUMIKIN CHEMICAL Co.,Ltd. Patentee after: KUKDO CHEMICAL Co.,Ltd. Address before: Han Guoshouer Co-patentee before: NIPPON STEEL & SUMIKIN CHEMICAL Co.,Ltd. Patentee before: KUKDO CHEMICAL Co.,Ltd. |