CN100374480C - Process for producing aromatic polycarbonate - Google Patents

Process for producing aromatic polycarbonate Download PDF

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Publication number
CN100374480C
CN100374480C CNB2004800239498A CN200480023949A CN100374480C CN 100374480 C CN100374480 C CN 100374480C CN B2004800239498 A CNB2004800239498 A CN B2004800239498A CN 200480023949 A CN200480023949 A CN 200480023949A CN 100374480 C CN100374480 C CN 100374480C
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phenol
dpc
dihydroxyphenyl propane
bpa
manufacturing step
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CN1839170A (en
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兵头成俊
田中竜郎
早志功一
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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Abstract

A subject for the invention relates to a method for coping with by-product phenol in which the water content of the by-product PL generated in a PC production step is limited to a value in a given range to thereby maintain a production efficiency in the BPA production step and DPC production step to which the by-product PL is sent, whereby the overall efficiency of PC production is maintained. The invention is a process for producing an aromatic polycarbonate which comprises a diphenyl carbonate production step, a bisphenol A production step, and an aromatic polycarbonate production step, and is characterized in that the amount of water contained in the by-product phenol recovered in the aromatic polycarbonate production step is regulated to 0.2% by weight or smaller and this phenol is used as a starting material in the diphenyl carbonate production step and/or the bisphenol A production step.

Description

The manufacture method of aromatic copolycarbonate
Technical field
The present invention relates to the manufacture method of aromatic copolycarbonate.
Background technology
Aromatic copolycarbonate (hereinafter referred is " PC ") carries out the polyreaction manufacturing by diphenyl carbonate (hereinafter referred is " DPC ") and dihydroxyphenyl propane (hereinafter referred is " BPA ") usually.
[processing of by-product phenol]
In above-mentioned polyreaction, can produce phenol (hereinafter referred is " PL ") as by product.This by product PL comprises DPC, BPA, by one to several DPC molecules and impurity such as oligopolymer that form to several BPA molecules.The method that described by product PL is turned back to BPA manufacturing step or DPC manufacturing step is known.
That is, patent documentation 1 put down in writing with described by product PL directly or purifying become the method that turns back to the BPA manufacturing step after the low-purity.The low also passable reason of gained by product PL purification degrees is, that DPC or described oligopolymer are hydrolyzed generation is PL and BPA, so when these compounds enter the BPA manufacturing step, also without any problem.
In addition, patent documentation 2 and patent documentation 3 etc. have been put down in writing and by product PL is purified to high purity then it has been turned back to method in the DPC manufacturing step.The reason that gained by product PL should have high purification degrees is, need prevent that BPA etc. from entering in the DPC manufacturing step and result in blockage.
[connection of manufacturing step]
Usually use the BPA that will be in molten state behind the purifying to cool off the solid BPA that is obtained.But, being installed near in the situation of PC producing apparatus at the BPA producing apparatus, the BPA/PL mixing solutions that the BPA of above-mentioned molten state directly maybe will be able to be had definite composition directly is provided to above-mentioned PC producing apparatus and carries out polymerization.This method does not need to reheat or purifying, thereby has improved thermo-efficiency.
[liquid waste disposal]
In addition, DPC and BPA manufacturing step and PC manufacturing step produce the waste liquid that contains large amount of organic matter separately.
Particularly, at first in above-mentioned PC manufacturing step, waste liquid produces as follows.DPC and BPA are being made by polymerization procedure in the key step of PC as raw material, composition liquefaction and the process distilation steps that evaporates in the above-mentioned polymerization procedure reclaimed PL, the gained distillation leftover is waste liquid.Comprise PL, DPC, BPA in this distillation leftover, by DPC and several molecules of BPA in conjunction with oligopolymer of forming etc., the recovery of these compositions badly influences the yield of PC.
About this point, patent documentation 3 and patent documentation 4 disclose the method that above-mentioned distillation leftover is turned back to above-mentioned polymerization procedure, and patent documentation 1 disclose with above-mentioned distillation leftover carry out redistillation with reclaim above-mentioned each composition and with gained recovery/distillation leftover as the method for fuel.
In above-mentioned DPC manufacturing step, PL and carbonyl compound to be made in the key step of DPC by reactions steps and distilation steps as raw material, the distillation leftover that derives from distilation steps is waste liquid.This distillation leftover comprises DPC, thereby its recovery badly influences the yield of DPC.
About this point, patent documentation 5 discloses a kind of method, wherein, above-mentioned distillation leftover is carried out redistillation with recovery DPC, and this DPC is turned back in the liquid reaction mixture that is obtained by above-mentioned reactions steps.
In addition, in above-mentioned BPA manufacturing step, PL and acetone are used as raw material, are making by building-up reactions step, crystallisation step and solid/liquid separation step in the key step of BPA, obtaining the mother liquor that produces by above-mentioned solid/liquid separation step.As described in patent documentation 6, this mother liquor also comprises such as 2 except comprising a large amount of PL and BPA, by products such as 4-isomers, three phenols and chroman compounds, and further comprise a spot of coloring impurity and tint permanence impurity.Because this mother liquor comprises PL and BPA as the reaction raw materials of BPA, thus this mother liquor institute in steps in circulation and be repeated use.But, all do not circulate if mother liquor is not just handled, then can accumulate above-mentioned by product, coloring impurity and tint permanence impurity.Therefore need to remove these by products and impurity.
[vacuum apparatus]
In the DPC manufacturing step, reflux down by distillation purifying DPC.In the PC manufacturing step, PL and DPC are being carried out in the fractionation by distillation PL being removed.These distillation procedures use vacuum apparatus under reduced pressure to carry out, to reduce distillation temperature (seeing patent documentation 7).
[patent documentation 1] JP-A-2000-53759
[patent documentation 2] JP-A-10-60106
[patent documentation 3] JP-A-9-255772
[patent documentation 4] JP-A-9-165443
[patent documentation 5] JP-A-2002-322130
[patent documentation 6] JP-A-5-331088
[patent documentation 7] JP-A-9-38402
Summary of the invention
[the processing of by-product phenol; The problem of three manufacturing steps when merging]
Yet, in above-mentioned various situations,, water-content is not studied although all noticed content except water such as impurity such as BPA and DPC.Be included in as the DPC of polymer raw and the water among the BPA, especially those have been cured thereby have remained with water in the material of water, and all follow in by-product phenol with the water that polymerizing catalyst is supplied.In the BPA manufacturing step, the existence of water causes the decline of catalytic activity, has reduced transformation efficiency.In the DPC manufacturing step, the existence of water not only causes the decline of catalytic activity, but also causes the hydrolysis of the DPC of manufacturing.
In addition, the by-product phenol that produces at the PC polymerization procedure comprises above-mentioned impurity.Although comprising not having problems but being sent to, these by products understand bothersome impurity in the BPA manufacturing step in being sent to the DPC manufacturing step.These by products further comprise the impurity opposite with afore-mentioned.
In addition, as mentioned above, need a step, so as from the PC polymerization procedure the isolated phenol that comprises remove water in the composition as distillating of main component.Yet, DPC manufacturing step, BPA manufacturing step and PC manufacturing step are being merged so that in the situation that carry out in a place, because the BPA manufacturing step also has the step of removing water, therefore exist two or more to remove the step of water.
[connection between manufacturing step]
In the BPA manufacturing step gained BPA is carried out in the crystalline step, solid is easy to separate out on crystallization apparatus etc. and position that liquid contacts.Therefore need just stop this step and clean every the several months.Therefore, those steps from the building-up reactions step to crystallisation step in the BPA manufacturing step are intermittently carried out.
On the contrary, the DPC manufacturing step does not then have the problems referred to above, and DPC can make continuously.Therefore, when keeping BPA to be in molten state,, can be used for the polyreaction that PC makes continuously by storing the BPA of necessary amount.
Yet, when BPA is remained on molten state, causing xanthochromia and decomposition etc. easily, this has influenced the quality of gained PC.
[liquid waste disposal]
In addition, because the distillation leftover that obtains contains PL, when whole residues are turned back to polymerization procedure, can when beginning, polymerization influence the speed of starting polymerization in above-mentioned PC manufacturing step because of PL with regard to existence.And, because the distillation leftover that obtained is painted usually in the PC manufacturing step, does not carry out any processing and this residue is reclaimed, can cause the PC product to have color.Even if distillation leftover is carried out redistillation, gained recovery/distillation leftover also can comprise a spot of described each composition.Therefore, discarding this residue without any processing not only influences manufacturing efficient, but also can cause the problem of relevant carrying capacity of environment.
In addition, the distillation leftover that is obtained in the above-mentioned DPC manufacturing step is directly discarded usually.Because this residue still contains DPC, discarding this residue without any processing not only influences manufacturing efficient, but also may cause the problem of relevant carrying capacity of environment.
[vacuum apparatus]
In addition, when under reduced pressure distilling, following situation can appear: distillate composition such as PL and DPC etc. and extracted out by vacuum apparatus, form the liquid substance that is detained in the pipe section that connects vacuum apparatus, maybe the composition that distillates of this delay solidifies, thereby can not keep vacuum state.In addition, make in the situation of composition (for example PL and the DPC) backflow of separating,, return line is stopped up because the described composition that distillates solidifies in return line as overhead product at the employing pump.
Therefore, an object of the present invention is to provide the method for handling by-product phenol, wherein the water-content of the by product PL that produces in the PC manufacturing step is defined as the value of a specified range, the manufacturing efficient of BPA manufacturing step and the DPC manufacturing step of by product PL is sent in maintenance in view of the above, thus the overall efficiency that keeps PC to make.
The another one purpose is, difference according to the impurity that is comprised in the by-product phenol that produces in the aromatic copolycarbonate polymerization procedure, by-product phenol is delivered to diphenyl carbonate manufacturing step or dihydroxyphenyl propane manufacturing step, thereby make the purification process of by-product phenol more laborsaving.
Also have a purpose to relate to problem in the merging of three manufacturing steps, this purpose is, by adopting the existing step of making diphenyl carbonate and dihydroxyphenyl propane, make more laborsaving as the purification process that distillates composition of main component with the phenol that in the polymerization procedure of aromatic copolycarbonate, is produced.
The another one purpose relates to the connection between each manufacturing step, and the method for attachment between each manufacturing step that this purpose provides can provide the manufacture method of the PC of enough qualities.
Also have a purpose to relate to the method for liquid waste disposal, this purpose is, distillation leftover by will deriving from the DPC manufacturing step and the distillation leftover that derives from the PC manufacturing step turn back to the specific position in each step that PC makes, thereby improve overall efficiency and reduce carrying capacity of environment.
Also have a purpose to relate to distilation steps, this purpose is, in the device that PL or DPC are separated as overhead product, prevents to form the liquid substance retention or solidify in pipeline.
As the method for handling by-product phenol, the invention provides the method for making aromatic copolycarbonate (PC), this method comprises: diphenyl carbonate (DPC) manufacturing step wherein is used as raw material to make diphenyl carbonate (DPC) with phenol (PL) and at least a carbonyl compound; And/or the dihydroxyphenyl propane manufacturing step, wherein phenol (PL) and acetone are used as raw material to make dihydroxyphenyl propane (BPA); And aromatic copolycarbonate (PC) manufacturing step, wherein diphenyl carbonate (DPC) and dihydroxyphenyl propane (BPA) are used as raw material, make aromatic copolycarbonate (PC) by the PC polymerization procedure, and recovery by-product phenol, it is characterized in that, regulate water content in the by-product phenol that reclaims in described aromatic copolycarbonate (PC) manufacturing step for being equal to or less than 0.2 weight %, and with the part material of described phenol as diphenyl carbonate (DPC) manufacturing step and/or dihydroxyphenyl propane (BPA) manufacturing step.
In above-mentioned diphenyl carbonate (DPC) manufacturing step, as the phenol of raw material can be the phenol (PL) that contains by weight for the cresols of 20ppm～1000ppm and/or xylenol, and the phenol (PL) that produces in the polymerization procedure in above-mentioned aromatic copolycarbonate (PC) manufacturing step can be used as at least a portion that is used as the phenol of raw material in dihydroxyphenyl propane (BPA) manufacturing step.
In addition, described method is characterised in that, the phenol that produces as by product in the above-mentioned aromatic carbonate manufacturing step of 50 weight %～95 weight % is used as at least a portion of the phenol that uses in the above-mentioned diphenyl carbonate manufacturing step, and will be used as at least a portion of the raw material in the above-mentioned dihydroxyphenyl propane manufacturing step in the above-mentioned aromatic carbonate manufacturing step of 50 weight %～5 weight % as the phenol of by product generation.
For the connection between each step, its method is characterised in that, before above-mentioned PL distilation steps and/or carry out PC afterwards and store step, wherein store liquefaction thing that carries out the PC evaporation composition before the above-mentioned PL distilation steps and/or the by-product phenol that in above-mentioned PL distilation steps, is reclaimed; After above-mentioned DPC distilation steps, carry out DPC and store step, wherein be stored in the diphenyl carbonate that is obtained in this DPC distilation steps; And/or the BPA that stores the mixture of dihydroxyphenyl propane and phenol between above-mentioned BPA crystallization/separation step and above-mentioned PC polymerization procedure stores step.The method is characterized in that as required, employed hold tank has specified vol shown below in corresponding storage step.
10≤(Vc/Fc)≤100 (1)
(in expression formula (1), Vc represents the capacity (m of PC hold tank 3), Fc represents the liquefaction thing of PC evaporation composition or the feed rate (m of by-product phenol 3/ hr) (meter 3/ hour).)
10≤(Vd/Fd)≤100 (2)
(in expression formula (2), Vd represents the capacity (m of DPC hold tank 3), Fd represents the feed rate (m of diphenyl carbonate 3/ hr).)
10≤(Vb/Fb)≤1000 (3)
(in expression formula (3), Vb represents the capacity (m of BPA hold tank 3), Fb represents to be fed to the feed rate (m of the dihydroxyphenyl propane in the PC polymerization procedure 3/ hr).)
For method for treating waste liquid, the method is characterized in that, the PL distillation leftover is sent to DPC distilation steps and/or DPC recovery/distilation steps, PL distillation leftover and/or DPC distillation leftover and/or DPC recovery/distillation leftover are sent to above-mentioned BPA mother liquor treatment step, perhaps the PL distillation leftover is sent to above-mentioned DPC distilation steps and/or DPC recovery/distilation steps, subsequently, DPC distillation leftover and/or DPC recovery/distillation leftover are sent to above-mentioned BPA mother liquor treatment step.
In addition, for distilation steps, its method is characterised in that, for the distillation tower in DPC distilation steps or the PL distilation steps be provided for the condensation overhead product condenser, be used to the valve tube that reduces the vacuum apparatus of system pressure and connect described condenser and described vacuum apparatus, and described valve tube is had a down dip to described vacuum apparatus side direction by described condenser side, and is equal to or less than 1m by the total height that described condenser side rises part on the vacuum apparatus side direction.
Description of drawings
Fig. 1 is the schema that shows the example of DPC manufacturing step of the present invention.
Fig. 2 is the schema that shows the example of BPA manufacturing step of the present invention.
Fig. 3 is the schema that shows the example of the water sepn step (step (b-2)) in the BPA manufacturing step of the present invention.
Fig. 4 is the schema that shows the example of the mother liquor treatment step (step (g)) in the BPA manufacturing step of the present invention.
Fig. 5 is the schema that shows the example of PC manufacturing step of the present invention.
Fig. 6 is the schema that shows another example of PC manufacturing step of the present invention.
Fig. 7 shows according to DPC manufacturing step of the present invention, BPA manufacturing step and PC to make
Step comprises that DPC stores step, BPA and stores the schema of example that step and PC store the situation of step.
Fig. 8 is presented in DPC manufacturing step of the present invention, BPA manufacturing step and the PC manufacturing step, and PL distillation leftover (X2), DPC distillation leftover (X1) and DPC recovery/distillation leftover (X1 ') are sent to the schema of example of the embodiment of particular step.
Fig. 9 is the figure that shows reflux of the present invention.
The numerical markings in the accompanying drawing and the implication of symbol are as follows: 1DPC reactor, 2 desalination acid towers, 3 tempering tanks, 4 alkali neutralizing wells, 5 washing baths, 6 the one DPC distillation towers, 7 the 2nd DPC distillation towers, 8 DPC recovery/distillation towers, 11BPA PL withdrawing can, the 12PL knockout tower, 13 phenol vaporizers, 14 residue reactors, 15 regeneration reactors, 21 tempering tanks, 22 first polymerization tanks, 23 second polymerization tanks, 24 trimerization grooves, 25 the 4th polymerizers, 26 heat exchangers, 27 heat exchangers, 28 condensers, 29PC PL withdrawing can, 29a the one PC PL withdrawing can, 29b the 2nd PC PL withdrawing can, 30 the one PL distillation towers, 31 the 2nd PL distillation towers, 32 forcing machines, 33a and 33b reflux, 41 distillation towers, 42 condensers, 43 vacuum apparatuss, 44 vacuum-liness, 45 condensate drums, 46 liquid-feeding pumps, 47 return lines, 48 smoke collectors, 49 leakage fluid drams, 50 supplying openings, 51 valves, 52 valves, 53 leakage fluid drams, 54 leakage fluid drams, 55 supplying openings, 56 valves, 57 conveying ends, A acetone, BPA dihydroxyphenyl propane, the C1 alkali catalyst, the C2 alkaline catalysts, CDC phosgene, D1 hydrogen chloride gas, D2 is through neutral waste water, D3 waste water, the low overhead product that boils of D4BPA, D5 discharges gas, the low overhead product that boils of D6PC, the D7 waste liquid, AW water/acetone mixture, DPC diphenyl carbonate, the E1 alkaline aqueous solution, the F gas mixture, I acid, J additive, pPC evaporates composition, p1 the one PC evaporates composition, and p2 the 2nd PC evaporates composition, PL phenol, the s-PL by-product phenol, W water, X1DPC distillation leftover, X1 ' recovery/distillation leftover, the X2PL distillation leftover, mark a contains the liquid reaction mixture of DPC, and b is through the liquid of desalination acid, and d contains the recovery liquid of DPC, e is through neutral liquid, the liquid of f through washing, g first distillation leftover, kPL reclaims liquid, pPC evaporates composition, and q fs residue.
Embodiment
Below will describe in detail embodiment of the present invention.
Method according to manufacturing aromatic copolycarbonate of the present invention (PC) is that diphenyl carbonate (DPC) and dihydroxyphenyl propane (BPA) are carried out polymerization to make the method for described polymkeric substance.
[DPC manufacturing step]
DPC is made as raw material by PL and at least a carbonyl compound.To described carbonyl compound without limits, as long as it can form the carbonyl group of DPC.The example of described carbonyl compound comprises phosgene (hereinafter referred is " CDC "), carbon monoxide, dialkyl carbonate etc.It below is the explanation that relevant CDC is used as carbonyl compound and makes the step of DPC by DPC washing step and DPC distilation steps after reaction.
Above-mentioned DPC manufacturing step is made up of process shown in Figure 1.That is, the DPC reactions steps imports PL and CDC in the DPC reactor 1 and carries out as raw material and with alkali catalyst (C1) (for example pyridine).Although the reaction conditions in this step is not particularly limited, this reaction is preferably carried out under 50 ℃～180 ℃ and non-pressurized condition, and PL is in molten state under this condition.From the angle of CDC completely consumed, the preferred corresponding every mole of PL of the blending ratio of PL and CDC (mol ratio), the amount of CDC is 0.40 mole～0.49 mole.
The liquid reaction mixture a that contains DPC of DPC reactions steps manufacturing delivered to carry out desalination acid step in the desalination acid tower 2.The hydrochloric acid gas (D1) that produces in DPC reactor 1 and the desalination acid tower 2 is reclaimed and delivers to (not shown) in the salt acid treatment step.
Subsequently, make gained through the acid-treated liquid b process of desalination DPC washing step.This DPC washing step is made up of following neutralization procedure and water-washing step.That is, carry out neutralization procedure, wherein be sent in the tempering tank 3, deliver to then in the alkali neutralizing well 4, the hydrochloric acid that is not removed residual in the above-mentioned desalination acid tower is neutralized by alkaline aqueous solution (E1) through the acid-treated liquid b of desalination.That emits is sent in the wastewater treatment step (not shown) through neutral waste water (D2) herein, to reclaim the useful organic composition that is wherein comprised, makes it through active sludge treatment then.
Carry out the DPC water-washing step then, wherein the liquid e through neutralizing treatment of gained is sent in the washing bath 5, and water (W) washing.The waste water (D3) of emitting at this DPC water-washing step can be used as the alkali diluent, utilizes in the adjusting of the alkaline aqueous solution (E1) that aforementioned neutralization procedure uses again.
The water lotion f that obtains in the DPC water-washing step is delivered in the distillation tower that carries out the DPC distilation steps.Although Fig. 1 has used 3 distillation towers, this step is not limited to this pattern.In the situation of using 3 distillation towers, a DPC distillation tower 6 is used to reclaim the gas mixture (F) that comprises water, PL and alkali catalyst.Each component separating of this gas mixture (F) can be utilized in reactive system then again.
The first distillation leftover g that in the 2nd DPC distillation tower 7 a DPC distillation tower 6 is emitted carries out redistillation, and reclaiming product with the form of overhead product is purified DPC.
There is no particular limitation to the distillation condition of a DPC distillation tower 6, and DPC can stay as long as water, alkali catalyst and PL can be steamed.1.3kPa the pressure of～13kPa is preferred.Employed temperature is the boiling point under this pressure.On the other hand, there is no particular limitation to the distillation condition of above-mentioned the 2nd DPC distillation tower 7, and the boiling point impurity higher than DPC can stay as long as DPC can be steamed.1.3kPa the temperature of the pressure of～6.5kPa and 150 ℃～220 ℃ is preferred.
Subsidiary mention be, the DPC distillation leftover X1 that emits from the 2nd DPC distillation tower 7 contains impurity, this impurity mainly contain with phenol in the methyl substituted DPC derivative that forms of impurity methylphenol reaction and the bromine substituent of the DPC that forms with the bromine reaction that remains among the CDC.But this DPC distillation leftover X1 further contains DPC itself.Therefore, can this DPC distillation leftover of redistillation X1, to reclaim diphenyl carbonate (DPC).In this case, adopt 8 pairs of DPC distillation leftovers of DPC recovery/distillation tower X1 as shown in Figure 1 to reclaim/distilation steps.Therefore, the recovery liquid d that contains DPC can reclaim by distillation.Like this, reclaimed DPC recovery/distillation leftover (X1 ') from the distillation tower bottom, the DPC derivative that methyl substituted in the described DPC recovery/distillation leftover (X1 ') and bromine replace is concentrated.
There is no particular limitation to the distillation condition of above-mentioned DPC recovery/distillation tower 8, and the boiling point impurity higher than DPC can stay as long as DPC can be steamed.1.3kPa the temperature of the pressure of～6.5kPa and 150 ℃～220 ℃ is preferred.
The recovery liquid d that contains DPC owing to the overhead product from above-mentioned DPC recovery/distillation tower is the composition that contains a large amount of DPC, therefore by being sent in the tempering tank 3, this DPC can be recycled in washing/distilation steps, and (DPC) efficient that reclaims that further improves diphenyl carbonate.
[BPA manufacturing step]
The BPA manufacturing step is made up of method as shown in Figure 2.Promptly, PL and acetone (A) are used as raw material, remove step (step (b)), BPA crystallization/separation step (step (c)), heating/fusion step (step (d)), PL removal step (step (e)) and granulation step (step (f)) by BPA reactions steps (step (a)), BPA low boiling substance and make BPA.
Next step makes an explanation respectively to above-mentioned each step.
Step (a) is to make PL and acetone (A) pass through condensation reaction to obtain the step of BPA in the presence of acid catalyst.The PL and the acetone (A) that are used as raw material are herein reacted under the condition of PL amount greater than the chemical theory amount.The mol ratio of PL and acetone (A) than counting 3～30, is preferably 5～20 with PL/ acetone (A).Reaction is 30 ℃～100 ℃ in temperature usually, is preferably 50 ℃～90 ℃ and pressure and is generally normal pressure to 5 kg/cm 2.G carry out down.
As acid catalyst, can use for example mineral acid, organic acid or ion exchange resin etc. such as hydrochloric acid.In the situation that makes spent ion exchange resin as acid catalyst, degree of crosslinking is 1%～8%, and the Zeo-karb of preferred 2%～6% gel-type sulphonic form suits.Yet there is no particular limitation to ion exchange resin.Hydrochloric acid also can be used as acid catalyst.
Although can use the Zeo-karb of sulphonic form itself, can use the Zeo-karb that carries out the sulphonic form of modification as required.The example that is suitable for the compound of modification comprises the compound with mercapto groups.
As described compound with mercapto groups, can use the known any compound that is suitable for this application, for example amino alkanethiol (as 2-ethylamine mercaptan), ω-pyridyl alkanethiol (as 2-(4-pyridyl) ethane mercaptan) and have (as 2,2-dimethylthiazole alkane) such as thiazolidine compounds of sulfydryl by hydrolysis etc. easily.
The reaction mixture that obtains by above-mentioned steps (a) also comprises water (W) that unreacted PL, unreacted acetone (A), catalyzer and by product for example produce by reaction and coloring material etc. usually except comprising BPA.
Above-mentioned steps (b) is the step that BPA low boil composition and catalyzer (for example hydrochloric acid) are removed from the liquid reaction mixture that above-mentioned steps (a) obtains.Herein, the low composition that boils of BPA comprises water W, unreacted acetone (A) and boiling point and the approaching material of these materials that reaction produces.In this step, by for example underpressure distillation etc. these low compositions that boil are removed from above-mentioned reaction mixture, and waited removal solids component (for example catalyzer) by for example filtering.Have in the situation of reactor of fixed bed catalyst in employing, not necessarily need to remove catalyzer.In underpressure distillation, the preferred pressure and temperature that uses is respectively 50mmHg～300mmHg and 70 ℃～130 ℃.Unreacted PL wherein can appear through azeotropic and the situation that a part of PL is removed from system.
The BPA that evaporates in the above-mentioned steps (b) is low, and the overhead product (D4) that boils comprises water and small amount of acetone (A) and phenol (PL).As shown in Figure 3, described BPA is low, and the overhead product (D4) that boils is sent in the PL knockout tower 12,, adopts extraction agent in case of necessity here, carries out reclaiming at the bottom of tower the water sepn step (step (b-2)) of PL.The PL that obtains in this water sepn step reclaims liquid k and is recovered to BPA with in the PL withdrawing can 11.Otherwise processed is from the water/acetone mixture AW of above-mentioned PL knockout tower 12 recovered overhead.
Above-mentioned steps (c) is that the liquid mixture cooling that obtains in the above-mentioned steps (b) is carried out separation steps with the mixture of deposit B PA and PL and to this mixture.(c) is preceding in described step, and in the liquid mixture that obtains in above-mentioned steps (b), BPA concentration can be adjusted to 10 weight %～50 weight % by steaming or adding PL, is preferably 20 weight %～40 weight %.Can improve the yield of this affixture like this, and can regulate the apparent viscosity of paste mixture effectively, thereby improve operability, be preferred in this.The example of the mixture of above-mentioned BPA and PL comprises crystal and the BPA crystal and the PL crystalline simple mixtures of the affixture of BPA and PL.
Cooling in the above-mentioned steps (c) proceeds to 45 ℃～60 ℃ temperature usually, isolates the crystal of BPA/PL affixture or the crystal of compound separately in view of the above, thereby makes this system become pulpous state.Employing places outside heat exchanger or utilization to add the evaporation of water latent heat of partial crystallization device and removes heat and carry out described cooling.Subsequently, this paste liquid is filtered or centrifugation etc., be separated into crystal and contain the mother liquor of by product.This crystal is used for next step.By the BPA mother liquor treatment step (g) that is described further below with part or all of isolating Recycling Mother Solution in step (a), and used as part or all of the PL that uses as raw material, thereby realize the further raising of yield.
Above-mentioned steps (d) is the crystalline step that heating and fusion are obtained by above-mentioned steps (c).It is that 45 weight %～70 weight % and PL content are 55%～30% composition that this affixture crystal has BPA content usually.By being heated to 100 ℃～160 ℃ and these crystal of fusion are used for next step then.
Above-mentioned steps (e) is PL to be removed and obtains in view of the above the step of fused BPA from the melts that above-mentioned steps (d) obtains.Use method such as underpressure distillation from step (d) thus remove PL this affixture that dissociates the melts that obtains.Can reclaim highly purified BPA thus.Preferably the pressure of 10mmHg～100mmHg and 150 ℃～220 ℃ and the high at least 10 ℃ temperature of fusing point of the mixture of dihydroxyphenyl propane (the BPA)/phenol (PL) that exists in than system carry out underpressure distillation.Except underpressure distillation, also proposed to adopt stripping to remove the method for residual PL.
Above-mentioned steps (f) is that the fusion BPA cools/solidifies that obtains in will above-mentioned steps (e) and granulation are to obtain the step of granular product.Adopt tablets press (for example spray-dryer), make fused BPA form drop and cools/solidifies and obtain product.By described drops of preparation such as spraying, drippage, spreadings, adopt nitrogen, air etc. to cool off usually.
In this BPA manufacturing step, especially in above-mentioned steps (a), synthesized simultaneously with BPA and to have comprised 2,4 '-dihydroxyphenyl propane is interior by product (calling " BPA by product " in the following text).These BPA by products mainly are present in the mother liquor that obtains in the above-mentioned steps (c), and circulate at the BPA manufacturing step.Therefore, above-mentioned BPA by product easily accumulates in this recycle system.When the BPA byproducts build-up to or have following tendency when being higher than certain degree: the deficiency that becomes of the separation in the above-mentioned steps (c), this by product is partly followed one side at BPA, causes the decline of BPA product quality.Therefore, the mother liquor that part or all of above-mentioned steps (c) is obtained carries out BPA mother liquor treatment step (step (g)), in view of the above the above-mentioned BPA by product of separation/removal from this mother liquor.To reduce the manufacturing raw material of the described mother liquor of BPA by product thus, can keep the quality of BPA thus as BPA.
Above-mentioned steps (g) is to reclaim the step of PL by distillation, or following steps: in the presence of alkaline matter, add hot mother liquor, be present in BPA by product in this mother liquor with decomposition, and obtain PL and PL derivative in view of the above, adopt acid catalyst or alkaline catalysts to make these compound reactions subsequently, reclaim this BPA then to make BPA.
Particularly, as shown in Figure 4, at first part or all of mother liquor and alkaline matter (for example sodium hydroxide or potassium hydroxide) are imported in the PL vaporizer 13 simultaneously.Subsequently, heat this content to the temperature that is not less than the PL boiling point, with evaporation PL, this PL is discharged by the top of PL vaporizer 13.Gained comprises BPA and the BPA by product is discharged by the bottom of PL vaporizer 13 as the evaporation residue of main component, and delivers to residue producer 14.Heat this residue to 180 ℃～300 ℃, make BPA and BPA by product generation decomposition reaction in view of the above, with the degradation production of the reaction intermediate isopropenyl phenol that obtains to comprise BPA.These degradation productions are distilled by cat head.On the other hand, (not shown) during liquid is sent to such as liquid waste disposal steps such as burning disposal as the waste liquid that contains large amount of organic matter at the bottom of the tower that produces in this residue reactor 14.
As the degradation production of BPA by product and PL that obtains and PL derivative steam by the top of residue reactor 14, and be sent in the regeneration reactor 15.In this operation, when PL and PL derivative took out by the top of residue reactor 14, they mixed with the PL that discharges from the top of above-mentioned PL vaporizer 13.The result has reduced the concentration of PL derivative, and can prevent the generation of unwanted side reaction.
Then, in regeneration reactor 15, adopt acid catalyst to make PL and PL derivative (they are degradation productions of BPA by product) secondary response again, obtain BPA etc. in view of the above.This reaction product and unreacted PL are mixed with the PL that is used as above-mentioned raw materials together, and deliver to step (a).Above-mentioned BPA directly reclaims by step (c), and because PL is used as raw material to be used, so can improve the manufacturing efficient of BPA.
[PC manufacturing step]
The PC manufacturing step is made up of method as shown in Figure 5.That is, DPC that will make by aforesaid method and BPA be as raw material, and import in the tempering tank 21 and mix with alkaline catalysts (C2) (for example alkaline aqueous solution etc.).The gained mixture is delivered to polymerization tank to carry out the PC polymerization procedure.There is no particular limitation to polymerization tank, as long as can carry out polycondensation when steaming the phenol that produces as polymeric by-products.Polymerization tank can be the groove that is selected from any type of vertical groove, horizontal groove and tower groove.
Number to polymerization tank is not particularly limited.But because polyreaction is the polycondensation of taking off phenol simultaneously, the two or more polymerization tanks of therefore preferred use are so that can change polymerizing condition according to the polymerization degree.Fig. 5 has shown one group of polymerization tank, and it is 3 vertical grooves (first polymerization tank 22, second polymerization tank 23 and the trimerization groove 24) and 1 horizontal groove (the 4th polymerizer 25), and these polymerization tanks are series connected.Polymerizing condition in this case for example comprises: the condition of first polymerization tank 22 is 200 ℃～250 ℃ and 50Torr (holder)～200Torr, the condition of second polymerization tank 23 is 230 ℃～280 ℃ and 10Torr～50Torr, the condition of trimerization groove 24 is 250 ℃～300 ℃ and 0.2Torr～5Torr, and the condition of the 4th polymerizer 25 is 260 ℃～320 ℃ and 0.05Torr～2Torr.When adopting described polymerizing condition, along with polymeric carries out, by-product phenol (hereinafter referred is " s-PL ") is steamed, and can obtain having the PC of the required polymerization degree in view of the above.
Adopt heat exchanger 26 and 27 and condenser 28 make produce in the above-mentioned PC polymerization procedure comprise the PC evaporation composition p liquefaction of s-PL as main component, be sent to PC with PL withdrawing can 29.To take out to the vacuum apparatus side and deliver to the treatment step (not shown) less than the exhaust (D5) of liquefaction.
The PC that makes in the PC polymerization procedure is delivered to forcing machine 32.In this forcing machine 32, contained volatile substances is removed as exhaust (D5), add sour I and various additive J simultaneously, with the neutralization of carrying out catalyzer etc.Then polymkeric substance is processed (for example granulation) (not shown), to obtain PC as product.
As mentioned above, liquefy above-mentioned PC evaporation composition p and be sent to PC with in the PL withdrawing can.Though PC evaporation composition p comprises s-PL as main component, they further comprise the oligopolymer that forms as the DPC of raw material and BPA, by the BPA polycondensation of the DPC of one or more molecules and one or more molecules, from the water of alkali catalyst etc.Therefore, this PC evaporation composition p is carried out the PL distilation steps to reclaim s-PL.The example of described PL distilation steps comprises the method for the distillation tower of two sections of uses as shown in Figure 5.At first, in a PL distillation tower 30, steam the boiling point composition lower that comprises water, get rid of and reclaim and contain water as main component and contain the low overhead product (D6) that boils of PC of PL than PL.Then, first section distillation leftover q in the PL distillation tower 30 delivered to the 2nd PL distillation tower 31, in the 2nd PL distillation tower 31, remove high boiling material matter and reclaim s-PL, and reclaim above-mentioned high boiling material matter PL distillation leftover (X2) by distillation.
[water-content of the processing 1:s-PL of by-product phenol (s-PL)]
Water-content among the s-PL that reclaims by distillation in the above-mentioned PL distilation steps is desirably and is equal to or less than 0.2 weight %, preferably is equal to or less than 0.1 weight %, more preferably is equal to or less than 0.05 weight %, further preferably is equal to or less than 0.01 weight %.If its content is greater than 0.2 weight %, as will be described later, this s-PL can cause the decline of catalyst activity in DPC manufacturing step and the BPA manufacturing step when being sent to above-mentioned DPC manufacturing step or BPA manufacturing step, and causes hydrolysis etc. in the DPC manufacturing step easily.Therefore, use described s-PL to cause making in DPC manufacturing step and the BPA manufacturing step decline of efficient easily.On the other hand, because water-content is the smaller the better, so the following 0 weight % that is limited to of water-content.
When attempting to steam water from the PC evaporation composition p of a PL distillation tower 30, when distilling under usual conditions, a large amount of PL and waters are followed, thereby cause loss.This is because water and PL have azeotropy.The technology that is used to reduce this loss comprises: carry out extractive distillation, adopt reduced pressure to eliminate azeotropy and increase the quantity and the reflux ratio of theoretical tray.In any situation, all can not thoroughly separate from the angle of economy.Therefore, can use following method: under the conventional distillation condition in a PL distillation tower 30 by water and part PL being steamed together the low overhead product (D6) that boils of the PC that obtains, the low overhead product (D6) that boils of this PC is delivered to DPC washing step and/or the water sepn step in the BPA manufacturing step (step (b-2)) in the above-mentioned DPC manufacturing step.
The distillation condition of an above-mentioned PL distillation tower 30 preferably includes: the pressure from normal atmosphere to the low pressure of tens of holders and be not less than water at the boiling point under this pressure and be not higher than the tower top temperature of the boiling point of phenol under this pressure.By the top of a PL distillation tower 30 expellant gas like this is the mixed gas of water/PL, preferably with the boiling point of top tower control to the mixed gas with target composition.If above-mentioned tower top temperature is lower than the boiling point of water, the water-content of fs residue q can rise, and the water-content that produces the s-PL that obtains in the 2nd PL distillation tower 31 may exceed the possibility of described scope.On the other hand, if above-mentioned tower top temperature is higher than the boiling point of PL, the amount that then is included in the s-PL in the low overhead product (D6) that boils of PC can increase, and causes its recovery to need lot of energy.Therefore such temperature is uneconomic.
Be specially by the PL content in the top expellant gas of an above-mentioned PL distillation tower 30: PL concentration preferably is equal to or greater than 50 weight %, is preferably especially to be equal to or greater than 70 weight % and to be equal to or less than 99.8 weight %.
With gained s-PL thus as the part of raw materials in DPC manufacturing step or the BPA manufacturing step.
Particularly, in above-mentioned DPC manufacturing step, s-PL is used for above-mentioned DPC reactions steps.When being sent to above-mentioned DPC reactions steps, s-PL can be as part or all of the PL of raw material.In this case, because its water-content is in above-mentioned scope,, thereby can keep the manufacturing efficient of DPC so the water that is included among the s-PL produces slight influence to reactions steps.
Next step, in above-mentioned BPA manufacturing step, s-PL is used for above-mentioned BPA reactions steps (step (a)).In above-mentioned BPA reactions steps, s-PL can be used as part or all as the PL of raw material.In this case, because its water-content is in above-mentioned scope,, thereby can keep the manufacturing efficient of BPA so the water that is included among the s-PL produces slight influence to synthetic reactions steps.
[processing of low overhead product (D6) that boil of PC]
As mentioned above, the low overhead product (D6) that boils of the PC that steams in the above-mentioned PL distillation tower 30 is turned back to DPC washing step or the water sepn step in the above-mentioned BPA manufacturing step (step (b-2)) in the above-mentioned DPC manufacturing step, thereby can reclaim the PL in the low overhead product (D6) that boils of PC.
Particularly, as shown in Figure 1, when the low overhead product (D6) that boils turns back in the DPC washing step (for example the alkali neutralizing well 4) in the above-mentioned DPC manufacturing step with PC, the PL that is included in the low overhead product (D6) that boils of PC is extracted in the organic phase (liquid reaction mixture), be recovered as the mixed gas (F) in next step the one DPC distillation tower 6, finally be used as the raw material of DPC.
On the other hand, as Fig. 2 or shown in Figure 3, when the water sepn step (step (b-2)) that the low overhead product (D6) that boils of PC is turned back in the above-mentioned BPA manufacturing step, more specifically, when for example turning back in the PL knockout tower 12, be included in PL in the low overhead product (D6) that boils of PC and be recovered with the form that PL reclaims liquid k at the bottom of the tower, at last as the raw material of BPA.
[the processing 2 of by-product phenol (s-PL); The processing of the PC evaporation composition in the PC polymerization procedure]
As shown in Figure 5, adopt heat exchanger 26 and 27 and the PC evaporation composition p that contains by-product phenol that in above-mentioned polymerization procedure, produces of condenser 28 liquefaction, and be sent to PC with PL withdrawing can 29.The treatment step (not shown) is delivered in the exhaust (D5) of liquefaction not yet.
Incidentally, the 24 evaporation constituents mixts that obtain are different mutually at impurity except by-product phenol from above-mentioned first polymerization tank 22 to the trimerization groove respectively.Particularly, the impurity that comprises except by-product phenol in the evaporation composition that the polymerization procedure at initial stage is discharged has such as impurity such as the boiling point impurity lower than PL, a spot of carbonyl compound, diphenyl carbonates.These impurity are to be used for the raw material of above-mentioned DPC manufacturing step and the reaction product that obtains in this step, wherein do not comprise such as high boiling point materials such as BPA.Therefore, the evaporation composition that comprises these impurity does not need purifying, or after being purified to low-purity, promptly can be used as the part of the PL of DPC manufacturing step use.
On the other hand, the impurity that comprises except by-product phenol in the evaporation composition of being discharged by the polymerization procedure in above-mentioned PC polymerization procedure later stage has the boiling point impurity higher than PL, for example DPC, BPA and the oligopolymer that formed by DPC and BPA etc.Wherein comprise the boiling point impurity lower hardly than PL.The hydrolysis and become the raw material and the reaction product of this manufacturing step in the BPA manufacturing step of these impurity.Comprise alcohols that causes the catalyst activity reduction in the BPA manufacturing step etc. hardly.The evaporation composition that comprises described impurity does not need purifying, or after being purified to low-purity, promptly can be used as the part of the PL of BPA manufacturing step use.
Therefore, as shown in Figure 6, the evaporation composition of discharging at the PC polymerization procedure can reclaim by two parts.That is to say, the evaporation composition that discharges in the initial stage polymerization procedure promptly from the PC evaporation composition p1 that contains by-product phenol of first polymerization tank 22 or recovery from first polymerization tank 22 and second polymerization tank 23, can be delivered to a PC with among the PL withdrawing can 29a.In addition, can be with the evaporation composition that discharges in the later stage polymerization procedure, promptly, deliver to the 2nd PC with among the PL withdrawing can 29b from later polymerization tank of second polymerization tank 23 or the 2nd PC evaporation composition p2 that comprises by-product phenol that from the later polymerization tank of trimerization groove 24, reclaims.
The PC evaporation composition p1 that so reclaims does not need to carry out PL distilation steps as shown in Figure 5, promptly can be as a part that is used as the PL of raw material in the DPC manufacturing step.On the other hand, the 2nd PC evaporation composition p2 does not need to carry out PL distilation steps as shown in Figure 5, promptly can be as a part that is used as the PL of raw material in the BPA manufacturing step.
Preferably, at the one or more polymerization tanks that are used for obtaining being used to the PC evaporation composition p1 that contains by-product phenol of above-mentioned DPC manufacturing step, promptly on first polymerization tank 22 or first polymerization tank 22 and second polymerization tank 23, being provided for liquefies and reflux partly evaporates the reflux 33a and the 33b of composition.By this reflux 33a and 33b are set, distillating in the composition in taking from first polymerization tank 22 or first polymerization tank 22 and second polymerization tank 23, the composition that boiling point is higher than PL can turn back in the corresponding polymerization tank.The result can further reduce the boiling point components in proportions higher than PL of gained among the PC evaporation composition p1.
Incidentally, the evaporation composition that reclaims from above-mentioned second polymerization tank 23 is sent to PC PL withdrawing can 29a or the 2nd PC PL withdrawing can 29b as mentioned above.For the selection of this withdrawing can, can only give one of these two withdrawing cans installation pipeline.As an alternative, as shown in Figure 6, can install respectively and reclaim tank connected pipeline and on corresponding pipeline, valve 34a and 34b are installed, can suitably switch pipeline thus with described two.It is the reasons are as follows.Except by-product phenol, the amount that is included in the impurity in the evaporation composition that reclaims in above-mentioned second polymerization tank 23 is less relatively.Therefore these can be evaporated composition as PC evaporation composition p1 or as the 2nd PC evaporation composition p2.
When the evaporation composition as overhead product that will obtain from above-mentioned second polymerization tank 23 is transported to PC usefulness PL withdrawing can 29a or the 2nd PC usefulness PL withdrawing can 29b, according to amount from the evaporation composition of other polymerization tank, especially be included in the amount of the by-product phenol in these evaporation compositions and be included in the amount that these evaporate the impurity in compositions, the amount of regulating the described evaporation composition that to carry.
Amount with respect to the whole by-product phenols that contain in the evaporation composition that in above-mentioned PC polymerization procedure, obtains, promptly be included in the total amount of the by-product phenol among PC evaporation composition p1 and the 2nd PC evaporation composition p2, in the amount of the by-product phenol that is comprised in the evaporation composition that in above-mentioned PC polymerization procedure, obtains, above-mentioned DPC manufacturing step will be sent to and as the amount of the part of raw material PL, promptly be included in the amount of the by-product phenol among the PC evaporation composition p1, be desirably 50 weight %～95 weight %, be preferably 50 weight %～70 weight %.
On the other hand, amount with respect to the whole by-product phenols that contain in the evaporation composition that in above-mentioned PC polymerization procedure, obtains, the amount that is included in the by-product phenol among above-mentioned the 2nd PC evaporation composition p2 is desirably 50 weight %～5 weight %, is preferably 50 weight %～30 weight %.
Be lower than 50 weight % if be included in the amount of the by-product phenol among the above-mentioned PC evaporation composition p1, then boiling point can be sneaked among the 2nd PC evaporation composition p2 than the low impurity of DPC especially alcohol etc.Without any processing described the 2nd PC evaporation composition p2 is used for BPA as raw material and makes, easily cause the decline of reactive behavior.Therefore the amount of such by-product phenol is unfavorable.On the other hand, if its amount is higher than 95 weight %, then may makes boiling point BPA and the oligopolymer higher sneak into PC evaporation composition p1, thereby cause line clogging in the DPC manufacturing than DPC.
The evaporation composition that uses in above-mentioned DPC manufacturing step is that the content of boiling point contained among the above-mentioned PC evaporation composition p1 high boiling compound higher than DPC (for example BPA and the oligopolymer that obtained by DPC and BPA) is preferably and is equal to or less than 1.0 weight %, more preferably is equal to or less than 0.1 weight %.If its content is higher than 1.0 weight %, then in DPC makes line clogging might take place.
In addition, the evaporation composition that in above-mentioned BPA manufacturing step, uses be boiling point contained among above-mentioned the 2nd PC evaporation composition p2 low-boiler lower than DPC (for example carbonyl compound and by the carbonyl compound deposits yields as the alcohol of by product etc.) content be preferably by weight and be equal to or less than 100ppm, more preferably be equal to or less than 50ppm.Incidentally, the PL that is used as raw material in above-mentioned BPA manufacturing step contains the by-product phenol that is included among above-mentioned PC evaporation composition p1 and above-mentioned the 2nd PC evaporation composition p2, and further comprises to be used for replenishing and exposed be purchased phenol and by BPA manufacturing step round-robin PL.Therefore, be used as among the PL of raw material above-mentioned, the content of above-mentioned low-boiler is lower than the content of the above-mentioned low-boiler in the by-product phenol, and by weight, the content of above-mentioned low-boiler is generally and is equal to or less than 20ppm, preferably is equal to or less than 5ppm.If its content is higher than 20ppm by weight, then exist low-boiler reduce BPA in making catalyst activity and the possibility that causes productive rate to descend.
At above-mentioned carbonyl compound is in the situation of dialkyl carbonate and/or carbonate alkyl aryl ester, and the above-mentioned alcohol as by product by the carbonyl compound deposits yields is the alkyl alcohol that is obtained by dialkyl carbonate and/or carbonate alkyl aryl ester.
Evaporate composition p by so reclaim PC with two portions, and carry described two portions to DPC manufacturing step and BPA manufacturing step, can omit the PL distilation steps in the PC manufacturing step, and help to improve manufacturing efficient according to the kind of impurity.
[the processing 3 of by-product phenol (s-PL); Distinguish the method for using PC evaporation composition p and being purchased PL according to impurity]
Incidentally, have in the situation of identical scale with BPA manufacturing step and PC manufacturing step at the DPC manufacturing step, the amount of the s-PL that produces in PC manufacturing step as shown in Figure 5 is about half of total amount of the PL that is used as raw material in DPC manufacturing step and the BPA manufacturing step in theory, and the amount of PL that is used as raw material in the DPC manufacturing step is in theory with to be used as the amount of PL of raw material identical in the BPA manufacturing step.Exposed by being purchased PL additional (hereinafter referred to as " being purchased PL ").Therefore, there is the situation of how using s-PL and being purchased the problem of PL.
Usually, be purchased PL and comprise a certain amount ofly, and in reclaim the PC evaporation composition p of s-PL without distillation, descended such as the content of impurity such as cresols and/or xylenol and pyruvic alcohol such as impurity such as cresols and/or xylenol and pyruvic alcohols.Therefore, can determine how to use s-PL based on difference such as the content of impurity such as cresols and/or xylenol and pyruvic alcohol.
Particularly, the PL that preferably is used as raw material in the DPC manufacturing step contains the cresols of 20ppm～1000ppm by weight and/or the phenol of xylenol (hereinafter referred to as " PL that contains cresols "), and the PL that is used as raw material in the BPA manufacturing step contains the cresols that is lower than 20ppm by weight and/or the phenol (hereinafter referred to as " PL of no cresols ") of xylenol.
The example that contains the PL of cresols comprises and is purchased PL.This is purchased PL except containing above-mentioned cresols and xylenol, also contains by weight to cause painted impurity for tens of ppm such as pyruvic alcohol etc.
As mentioned above, this PL that contains cresols etc. can directly be used in the above-mentioned DPC reactions steps.All be in the scope that the DPC reactions steps allows in this amount that contains each impurity among the PL of cresols etc. (for example cresols, xylenol and cause painted impurity (as pyruvic alcohol)).By the processing of being carried out in the DPC distillation tower 6 described later, described impurity is as the part of gas mixture F and steam or remove as distillation residue.Therefore, be used for above-mentioned PC manufacturing step, also do not influence the quality of gained PC even if employing is contained the DPC that the PL of cresols etc. makes.
The example of the PL of no cresols comprises the PC evaporation composition p that reclaims s-PL without distillation.The content of the catalyst toxicity impurity (for example pyruvic alcohol) among this PC evaporation composition p preferably is lower than 10ppm, more preferably less than 5ppm, especially preferably is lower than 1ppm.Its amount is not less than the remarkable shortening that 10ppm can cause catalyst life.
Such as cresols, xylenol and catalyst toxicity impurity or cause painted impurity for example the impurity such as pyruvic alcohol, the example that is included in the impurity among the above-mentioned PC evaporation composition p also comprises DPC, BPA and reacts the oligopolymer that forms by the BPA of the DPC of one or more molecules and one or more molecules except above-mentioned.
The cresols among the above-mentioned PC evaporation composition p and/or the content of xylenol preferably are equal to or less than 20ppm by weight, more preferably are equal to or less than 10ppm by weight.If its amount is higher than 20ppm by weight, then there is the BPA derivative that produces the alkyl replacement and the possibility that causes BPA purity to descend.
Above-mentioned PC evaporation composition p contains water.The existence of water in the BPA manufacturing step causes the decline of catalyst activity, and therefore causes the decline of BPA productivity.Therefore need remove the step of water.For reaching this purpose, preferably above-mentioned PC evaporation composition p is removed the step of water, use composition p then in the step in the BPA manufacturing step (a).
Step as removing water can adopt above-mentioned water sepn step (step (b-2)) itself.That is, in Fig. 3, PC is evaporated composition p deliver in the PL knockout tower 12, to carry out the step that water is removed as raw material.Water/acetone mixture the AW that steams in this operation of otherwise processed.On the other hand, the distillation leftover in the above-mentioned PL knockout tower 12 is delivered to high boiling material matter remove tower, but described high boiling material matter is removed tower not shown in Fig. 2 and 3.The high boiling material matter that is used to separate the boiling point composition higher than PL is then removed step, and the composition that in view of the above height boiled separates as deriving from liquid at the bottom of the distillatory tower/or removal, PL then is recovered as overhead product.
The PL that will so reclaim without any processing carries out the BPA reactions steps (step (a)) in the above-mentioned BPA manufacturing step as raw material.As an alternative, the PL of recovery can use in the PL withdrawing can 11 at above-mentioned BPA by temporary storage, carries out step (c) then as shown in Figure 2, and as required, carries out above-mentioned BPA reactions steps (step (a)) by mother liquor treatment step (step (g)).One of the reason that why will carry out above-mentioned BPA crystallization/separation step (step (c)) to the PL that reclaims is that using clean PL is ideal as the scavenging solution of synthetic BPA.Another reason is, even if the PL that reclaims has been carried out above-mentioned BPA crystallization/separation step (step (c)), the impurity that enters this step is 2 of the BPA that produces in above-mentioned BPA reactions steps, 4 '-(hereinafter referred to as " BPA by products ") such as isomerss, can not influence above-mentioned building-up reactions step this moment yet.On the other hand, the height that above-mentioned high boiling material matter removal step is discharged boils and becomes to be distributed to above-mentioned mother liquor treatment step (g), the useful composition of recovery in this step (g).
So, be purchased PL by PC being evaporated composition p delivers to the BPA manufacturing step and in the DPC manufacturing step, using, can reduce the disadvantageous effect of the impurity that comprised, and omit the PL distilation steps in the PC manufacturing step.Therefore can help to improve and make efficient.
[the connection between manufacturing step; Store the setting of step]
(1.PC manufacturing step)
In the PC manufacturing step, as shown in Figure 7, PC can and/or be set before above-mentioned PL distilation steps afterwards store step (PC first stores step or PC second stores step), described PC stores step and is used to store the liquefaction thing that carries out the preceding PC evaporation composition p of above-mentioned PL distilation steps, and/or is used for storing the s-PL that above-mentioned PL distilation steps reclaims.The described setting that this PC stores step has following effect.Even if when stopping or intermittently carrying out the PC polymerization procedure temporarily, above-mentioned PC evaporation composition p that stores in described storage step or s-PL also can be used as raw material PL and supply to subsequent step, be in PL distilation steps or DPC reactions steps or the BPA reactions steps, can move described subsequent step continuously thus.
Storing the capacity of the PC hold tank of step use can determine under the situation of the working time of considering above-mentioned PC polymerization procedure and stand-by time at PC.Particularly, described PC hold tank preferably has the capacity of the requirement of satisfying following formula (1) expression.
10≤(Vc/Fc)≤100 (1)
In expression formula (1), Vc represents the capacity (m of PC hold tank 3), Fc represents that the PC that liquefies evaporates the feed rate (m of composition or by-product phenol 3/ hr).
When Vc/Fc less than 10 the time, have the situation that is difficult to continuously above-mentioned PC evaporation composition p or s-PL are fed to next step.And, be difficult to regulate along with the PC manufacturing stage changes and variation that the PC evaporation composition p that causes forms.On the other hand, Vc/Fc can be greater than 100.But from making the viewpoint of efficient, because it is very little to store the necessity of so big amount, therefore the waste that excessive tankage caused is unwanted greater than the raising of making efficient, and from the viewpoint of thermostability, prolonged preservation also is disadvantageous.
Incidentally, described PC hold tank can only be stored installation in one of step in PC first storage row step and PC second, perhaps can be installed in separately in described two steps.Store in the step at a PC, the PC hold tank of a above-mentioned type can be installed, perhaps serial or parallel connection is installed two or more PC hold tanks.In two or more situations of described jar were installed, the Vc in the above-mentioned expression formula (1) represented the total volume of these jars of existing.
[2.DPC manufacturing step]
In the DPC manufacturing step, the DPC that is used for storing the DPC that the DPC distilation steps obtains stores step and can be arranged on as shown in Figure 7 after this DPC distilation steps.The setting that this DPC stores step has following effect.Even if when stopping or intermittently carrying out the DPC manufacturing step temporarily, this DPC stores the DPC that stores in step and also can be used as raw material DPC and be fed to subsequent step continuously, and promptly the PC manufacturing step can be made PC thus continuously.
Storing the capacity of the DPC hold tank that uses in the step can determine under the situation of the working time of considering above-mentioned DPC manufacturing step and stand-by time at above-mentioned DPC.Particularly, described DPC hold tank preferably has the capacity of the requirement of satisfying following formula (2) expression.
10≤(Vd/Fd)≤100 (2)
In expression formula (2), Vd represents the capacity (m of DPC hold tank 3), Fd represents the feed rate (m of diphenyl carbonate 3/ hr).
When Vd/Fd less than 10 the time, have the situation that is difficult to continuously above-mentioned DPC is fed to next step.On the other hand, Vd/Fd can be greater than 100.But, from making the viewpoint of efficient, owing to the necessity of storing so big amount is very little, the waste that excessive tankage club causes is greater than the raising of making efficient, therefore be unwanted, and from the viewpoint of thermostability, excessive tankage also is unwanted.
Incidentally, the DPC hold tank of a above-mentioned type can be installed, perhaps serial or parallel connection is installed two or more DPC hold tanks.In two or more situations of described jar were installed, the Vd in the above-mentioned expression formula (2) represented the total volume of these jars of existing.
[3.BPA manufacturing step]
In above-mentioned BPA manufacturing step, the BPA that is used to store the mixture of dihydroxyphenyl propane (BPA) and phenol (PL) stores step and can be arranged on PL as shown in Figure 7 and remove step (step (e)) afterwards, perhaps place above-mentioned BPA crystallization/separation step (step (c)) and PL to remove between the step (step (e)), but latter event does not illustrate in the drawings.
The setting that this BPA stores step has following effect.Even if the arbitrary step in temporarily stopping above-mentioned BPA manufacturing step and intermittently carry out during step before stopping step, this BPA stores the said mixture of storing in step and also can be fed in the PC manufacturing step, can make PC continuously thus.
Especially, above-mentioned BPA crystallization/separation step (step (c)) makes solid separate out on the crystallizer that comprises crystallizer tank and heat exchanger and part that liquid contacts easily.Therefore just need stop this step and clean every some months.Therefore, tend to intermittently carry out to the step the BPA crystallization/separation step (step (c)) from above-mentioned BPA reactions steps (step (a)).Therefore, above-mentioned BPA is stored step places PL to remove step (step (e)) afterwards, perhaps place above-mentioned BPA crystallization/separation step (step (c)) and PL to remove between the step (step (e)) (but latter event does not illustrate in the drawings), so, even if when carrying out above-mentioned BPA reactions steps (step (a)) to the step between the BPA crystallization/separation step (step (c)), the PC manufacturing step is carried out continuously on having a rest property ground.
Be stored in the liquid mixture etc. that example that above-mentioned BPA stores the mixture in the step comprises the crystallization of the affixture of BPA and PL, the affixture crystalline slurry that contains BPA and PL and BPA and PL.
The content that above-mentioned BPA/PL mixture has following composition: BPA usually is 45 weight %～70 weight %, and PL content is 55 weight %～30 weight %.Therefore, when the temperature in the above-mentioned storage process was 0～95 ℃, described affixture was a crystalline state.In the situation that the ratio of phenol is high in described mixture, when storage temperature is raised to when being equal to or greater than 40 ℃, the PL that exists with BPA affixture form does not become molten state.In this kind situation, described mixture is pulpous state or solution.And when storage temperature surpassed 95 ℃, described affixture dissolved and becomes molten state.
Above-mentioned storage temperature is preferably 45 ℃～150 ℃.It is desirable to above-mentioned BPA/PL mixture and be in pulpous state or solution state.In order to prevent that BPA from decomposing or painted purpose, preferably holds it in alap temperature.Under this condition, can suppress it is believed that to be to cause generation painted and decompose the material 4-isopropenyl phenol that obtains by BPA.
In addition importantly, the atmosphere in the hold tank should be such as atmosphere of inert gases such as nitrogen, to prevent to be mingled with air.Although can use austenitic stainless steel or ferritic stainless steel material usually as hold tank, the preferred low material of stripping that uses iron, the stripping meeting of iron reduces tone.Especially, have and be equal to or greater than 16% chromium content and be preferred more than or equal to the steel of 0.03% carbon content.For example, compare preferred use SUS304, compare with SUS316L or SUS304L and use SUS316 or SUS304 with SUS316.Certainly, it is more preferred to have the SUS309S and a SUS310S of higher chromium content.
The capacity that is used to store the jar of above-mentioned BPA/PL mixture can be determined under the situation of the working time of considering above-mentioned BPA manufacturing step and stand-by time.Particularly, described jar preferably satisfies the capacity of the requirement of following formula (3) expression.
10≤(Vb/Fb)≤1000 (3)
In expression formula (3), Vb represents the capacity (m of BPA hold tank 3), Fb represents to be supplied to the feed rate (m of the dihydroxyphenyl propane in the PC polymerization procedure 3/ hr).
When Vb/Fb less than 10 the time, have the situation that is difficult to carry out continuously the PC polymerization procedure.On the other hand, Vb/Fb can be greater than 1000.But from making the viewpoint of efficient, because it is very little to store the necessity of so big amount, therefore the waste that excessive tankage caused is unwanted greater than the raising of making efficient, and from the angle of quality, prolonged preservation also is unwanted.
Incidentally, the hold tank an of the type can be installed, perhaps serial or parallel connection is installed two or more hold tanks.In two or more situations of described jar were installed, the Vb in the expression formula (3) represented the total volume of these jars of existing.
Store in the step at above-mentioned BPA, owing to store the affixture of above-mentioned form, so when pH turned to an acid side or an alkaline side, decomposition reaction took place in BPA easily.In order to prevent the generation of described decomposition reaction, preferably BPA neutralization procedure (not shown) is placed the BPA hold tank that exists between above-mentioned BPA crystallization/separation step (step (c)) and the PC polymerization procedure, or place the step before these steps.The sour composition or the alkali composition that can in this BPA neutralization procedure, neutralize and exist in the described mixture.Suppress the decomposition of the BPA in the said mixture thus.
[liquid waste disposal]
(processing of PL distillation leftover (X2))
Oligopolymer that above-mentioned PL distillation leftover (X2) contains PL, DPC, BPA, formed by the BPA polycondensation of the DPC of one or more molecules and one or more molecules etc.Wherein, the amount of the PL that is comprised, DPC and BPA is very big.Therefore, in order to effectively utilize these useful components, as shown in Figure 8, above-mentioned PL distillation leftover (X2) is delivered to above-mentioned distilation steps or recovery/distilation steps in the above-mentioned DPC manufacturing step, or deliver to the above-mentioned mother liquor treatment step (step (g)) in the above-mentioned BPA manufacturing step.
In above-mentioned DPC manufacturing step, do not have above-mentioned recovery/distilation steps, and when above-mentioned PL distillation leftover (X2) delivered to above-mentioned distilation steps in the above-mentioned DPC manufacturing step, specifically, as shown in Figure 1, above-mentioned PL distillation leftover (X2) is delivered in the DPC distillation tower 6.As a result, above-mentioned PL distillation leftover (X2) is distilled in a DPC distillation tower 6 and the 2nd DPC distillation tower 7, and reclaims PL and DPC.Wherein, PL is recovered in a DPC distillation tower 6 as a kind of composition of gas mixture (F), and DPC is recovered in the 2nd DPC distillation tower 7.
When having above-mentioned recovery/distilation steps in the above-mentioned DPC manufacturing step above-mentioned PL distillation leftover (X2) being delivered to above-mentioned recovery in the above-mentioned DPC manufacturing step/distilation steps, specifically, as shown in Figure 1, above-mentioned PL distillation leftover (X2) is delivered in the DPC recovery/distillation tower 8.As a result, above-mentioned PL distillation leftover (X2) is distilled in DPC recovery/distillation tower 8, and reclaims PL and DPC, is sent to then in the tempering tank 3.Wherein, PL reclaims in a DPC distillation tower 6 as a kind of composition of gas mixture (F), and DPC reclaims at the 2nd DPC distillation tower 7.
In addition, when the above-mentioned mother liquor treatment step (step (g)) above-mentioned PL distillation leftover (X2) delivered in the above-mentioned BPA manufacturing step, specifically, as shown in Figure 4, above-mentioned PL distillation leftover (X2) is delivered in the residue reactor 14.As a result, PL steams with itself, and other composition then is decomposed, and obtains BPA and other compound in regeneration reactor 15 again.These compounds of gained are delivered in the BPA reactor (not shown) in the BPA manufacturing step.Therefore, PL is as raw material, and BPA and synthetic BPA move together.
(processing of distillation leftover (X1) or recovery/distillation leftover (X1 '))
In above-mentioned DPC manufacturing step, comprise DPC compounds impurity (for example DPC, methyl substituted DPC derivative and bromine replace DPC derivative) and other impurity in the distillation leftover (X1 ') that the distillation leftover (X1) that obtains maybe obtains when this DPC manufacturing step does not have recovery/distilation steps when this DPC manufacturing step has recovery/distilation steps.When above-mentioned PL distillation leftover (X2) being imported above-mentioned distilation steps or recovery/distilation steps, oligopolymer and other impurity that residue (X1) or (X1 ') further comprise BPA, formed by the BPA polycondensation of the DPC of one or more molecules and one or more molecules.In these impurity, the content of BPA and DPC is bigger.Therefore, in order to effectively utilize these useful components, above-mentioned distillation leftover (X1) or recovery/distillation leftover (X1 ') are delivered to above-mentioned mother liquor treatment step (step (g)) in the above-mentioned BPA manufacturing step.
In this kind situation, specifically, as shown in Figure 4, above-mentioned distillation leftover (X1) or recovery/distillation leftover (X1 ') are sent to residue reactor 14.As a result, these compositions are decomposed, and partially decomposed product is converted into BPA once more in regeneration reactor 15.The BPA of gained and phenol are delivered to BPA reactor (not shown) in the BPA manufacturing step.
(PL distillation residue (X2) and distillation leftover (X1) or recovery/distillation leftover (X1 '))
The example that is used to handle the method for PL distillation residue (X2), distillation leftover (X1) and recovery/distillation leftover (X1 ') comprises aforesaid method.Wherein preferable methods is, above-mentioned PL distillation residue (X2) are delivered to above-mentioned DPC distilation steps or DPC recovery/distilation steps, then with the DPC distillation leftover (X1) or the DPC recovery/distillation leftover (X1 ') that obtain in the above-mentioned DPC distilation steps) deliver to above-mentioned BPA mother liquor treatment step (step (g)).
By the described residue of processing like this, merge into the waste liquid (D7) that the above-mentioned mother liquor treatment step (step (g)) in dihydroxyphenyl propane (BPA) manufacturing step obtains by the waste liquid that DPC manufacturing step, BPA manufacturing step and PC manufacturing step are discharged.Therefore, obtain by described 3 steps respectively and the waste liquid that contains large amount of organic matter is merged into a kind of waste liquid, can reduce the amount of all waste liquids of discharge.Therefore, can carry out liquid waste disposal step (not shown) effectively, and can reduce its load.
[vacuum apparatus]
In above-mentioned DPC distilation steps, PC polymerization procedure and PL distilation steps such as on water distilling apparatus such as distillation tower and the poly-unit, be provided for condenser that condensation distillates composition, be used to the vacuum-lines that reduces the vacuum apparatus of system's internal pressure and connect above-mentioned condenser and vacuum apparatus.Hereinafter will be that example describes with the water distilling apparatus.As shown in Figure 9, be provided for the condenser 42 of condensation overhead product (for example DPC with PL etc.), the vacuum-lines 44 that is used to reduce the vacuum apparatus 43 of system's internal pressure and is connected above-mentioned condenser 42 and vacuum apparatus 43 for water distilling apparatus 41.
This water distilling apparatus 41 has the backflow part usually.The equipment that constitutes this backflow part comprises condenser 42, the condensate drum 45 that is used to collect the part phlegma that is used for the condensation overhead product, the liquid-feeding pump 46 that is used for the phlegma of condensate drum 45 is turned back to water distilling apparatus 41, and the return line 47 of connection liquid-feeding pump 46 and water distilling apparatus 41 etc.Hereinafter, described backflow part is called " reflux ".
Above-mentioned vacuum apparatus 43 is to be present in the gas in water distilling apparatus 41 and the reflux and to make water distilling apparatus 41 be in the equipment of vacuum state thus as drawing and discharging.The example of this vacuum apparatus 43 comprises vacuum pump.
The vacuum-lines 44 that is connected to this vacuum apparatus 43 is had a down dip to vacuum apparatus 43 side direction by condenser 42 sides.It is desirable to, in the horizontal component of vacuum-lines 44, the part with this inclination is long as far as possible.There is no particular limitation to above-mentioned obliquity, if with the inclination angle with horizontal direction be no more than greater than 0 ° 90 ° downward-sloping.But it is desirable to, horizontal direction is to the above-mentioned vacuum apparatus 2m that advances, and preferably advancing on above-below direction is equal to or greater than 1cm, and that better is the 5cm～1m that advances.Better is not have complete horizontal component or rising part on the horizontal component that tilts.Further even more ideal is that the inclination of whole vacuum-lines 44 is constant.Term " horizontal component " is meant part that is in horizontality and the part that is tilted a little by horizontality.Term " horizontal component fully " is meant and the vertical part of vertical direction.
Can have above-mentioned complete horizontal component or rising part in the described inclination.But the total height of rising part preferably is equal to or less than 1m, more preferably is equal to or less than 50cm, further preferably is equal to or less than 10cm.Most preferably, described inclination does not have above-mentioned this part.If the total height of rising part surpasses 1m, just there is following possibility: when overhead product is trapped in above-mentioned rising part, may cause the pressure-losses excessive, make its suction of can not reducing pressure fully.Term " rising part " is meant opposite with the above sloping portion part that is tilted to vacuum apparatus 43 side direction by condenser 42 sides.In described rising part, above-mentioned overhead product easily is detained as liquid or solid.When described overhead product was detained, it caused the loss of pressure.Overhead product is detained the obstruction that too much can cause pipeline itself.Therefore wish that vacuum-lines 44 does not have rising part.Therefore, even more ideal is that vacuum-lines is always had a down dip to vacuum apparatus 43 side direction by condenser 42 sides.
Above-mentioned condenser 42 condensation PL, DPC etc.Outside the overhead product discharge system of condensation, or be sent to condensate drum 45 in the above-mentioned reflux, in order to being back to water distilling apparatus 41.
Pressure in the above-mentioned distillation tower 41 is preferably decompression, and more preferably 1Torr～200Torr especially is preferably 5Torr～100Torr.When distillation tower 41 has when pressing in described, in the vacuum-lines 44 that the gas in the distillation tower 41 is extracted out, it is desirable to, the pressure behind the vacuum decompression is near or below the pressure in the distillation tower 41, more desirably is 1Torr～100Torr.
In addition, it is desirable to, the pipeline that extends to condenser 42 by the top of distillation tower 41 has and satisfies the following structure that requires.It is desirable to, the internal diameter of described pipeline makes that the linear velocity of real gas is 0.01m/sec (meter per second)～20m/sec.The length of pipeline that is extended to condenser 42 by the top of distillation tower 41 is short more good more.It is desirable to, its length is equal to or less than 10m, and better is to be 0m.In addition, the number of curved part is few more good more in the described pipeline.It is desirable to, its number is for being equal to or less than 5.According to above-mentioned requirements, it would be desirable that condenser 42 places the top of distillation tower 41 as overhead condenser.When satisfying described the requirement, distillation tower 41 has the more stable vacuum state that is formed by vacuum apparatus 43.
It is desirable to, the presentation mode of PL that steams and DPC gas is to be downward through condenser 42.
In addition, it is desirable to, the inside and the exit portion of condenser 42 have than major diameter, so that obtain lower gas line speed.If linear gas velocity is spent height, can cause the loss of pressure, and water distilling apparatus 41 might be remained on vacuum state.
It is desirable to, the smoke collector 48 that will be used to capture smog places between above-mentioned condenser 42 and the vacuum-lines 44.Its objective is and prevent that as far as possible PL or DPC smog from entering in the vacuum-lines 44 and delay therein or curing.
It is desirable to, above-mentioned vacuum-lines 44 has the equipment that is used to heat and its internal temperature is remained on the temperature of the fusing point that is not less than above-mentioned overhead product.The example of this equipment comprises that wherein vacuum-lines 44 has double-sleeve structure or has steam or the equipment of the structure of electric souffle access line.In the situation that above-mentioned overhead product is grouped into by two or more one-tenth, it is desirable to the fusing point that the pipeline 44 inner temperature that keep are not less than the highest material of fusing point.Though the inside of above-mentioned vacuum-lines 44 is in decompression state, the term of Shi Yonging " fusing point " is meant the fusing point of decompression state herein.When 44 inside, valve tube road remain on the fusing point that is not less than above-mentioned overhead product, uncooled and entered the PL of vacuum-lines 44 or DPC and uncured in condenser 42, but be in liquid state or gaseous state, can reduce the blocked possibility in vacuum-lines 44 inside in view of the above.Therefore from the angle of the operation of this step, the inside that it is desirable to vacuum-lines 44 remains on the temperature (this temperature is the fusing point of DPC) that is not less than 80 ℃, and is not higher than the head temperature of water distilling apparatus 41.
It is desirable to provides at least one leakage fluid dram 49 down for above-mentioned vacuum-lines 44.This is because being necessary to discharge has liquefied in vacuum-lines 44 or the overhead product of dewfall, and it is trapped in the vacuum-lines 44.It is desirable to, at least one described leakage fluid dram 49 is positioned at the part that is connected with vacuum apparatus 43 near vacuum-lines 44.It is the reasons are as follows.Because vacuum-lines 44 tilts, if the not leakage fluid dram discharge of the lowest part by as close as possible inclination pipeline of overhead product may cause overhead product to be detained in crossing the part of leakage fluid dram.This discharge opeing operation can not carried out in the process that adopts vacuum apparatus 43 to find time, but carries out after entire equipment stops.Length at vacuum-lines 44 surpasses in the situation of 3m, it is desirable to also at the middle part of vacuum-lines 44 leakage fluid dram 49 is set, because this can be avoided the delay of liquid easilier.
In addition, it is desirable to, the part that is positioned at above-mentioned condenser 42 sides on vacuum-lines 44 provides supplying opening 50, can provide heating fluid by this supplying opening.The position that it is desirable to this supplying opening 50 is as far as possible near condenser 42.Yet, in the situation of above-mentioned smoke collector 48 between vacuum-lines 44 and condenser 42, the position that it is desirable to supplying opening 50 is not between smoke collector 48 and condenser 42, but the part of connection smoke collector 48 on the as close as possible vacuum-lines 44.By supplying opening 50 is installed, above-mentioned heating fluid can import and discharges vacuum-lines 44 capable of washing thus by leakage fluid dram 49 by this supplying opening.Therefore it is desirable to the part 49 and should account for the longest as far as possible zone of vacuum-lines 44 from supplying opening 50 to leakage fluid dram.Owing to tilt, so will be more efficient from having than high potential energy one side supply.Therefore, it is desirable to 50 upward openings of the supplying opening in the vacuum-lines 44.
Above-mentioned heating fluid is to be the fluidic material under the temperature in vacuum-lines 44, and it can be liquid or gas.The example of above-mentioned heating fluid comprises water vapour, PL, nitrogen etc.Better is that above-mentioned heating fluid is water vapour or PL steam.This solid more preferably uses PL steam, because when even if DPC solidifies, also can dissolve in vacuum-lines 44.Heating fluid can be made up of a kind of described fluid or two or more described fluidic mixture.But, it is desirable to, under the temperature and pressure condition in vacuum-lines 44, above-mentioned heating fluid hardly with reactions such as the material of vacuum-lines 44 and DPC.Better is the fluid that does not react.
It is desirable to, above-mentioned vacuum-lines 44 has valve 51 and 52, and valve 51 and 52 is positioned at the part that vacuum-lines 44 is connected with condenser 42, vacuum apparatus 43, smoke collector 48 etc.This is because when cleaning vacuum-lines 44 with above-mentioned heating fluid, adopt these valves to isolate and can prevent that heating fluid from spilling from vacuum-lines 44.
It is desirable in addition, above-mentioned vacuum-lines 44 has the condenser of freezing (not shown).Better is to be installed in parallel two or more and to freeze condenser so that switch.It is ideal that one or more condensers are installed, and this is because can solidify the distillation composition that the device 42 of can not being condensed captures by force and collect, and the part that can suppress this vacuum-lines that freezes the condenser downstream 44 is stopped up or the pressure-losses strengthens.
In situation about from DPC, steaming, can also use placed in-line two or more condenser 42 effectively, to liquefy as overhead product from water distilling apparatus 41 expellant gas such as low-boiling compounds such as PL.In the case, preferably each condenser 42 is regulated, make along with the increasing of the distance of distillation tower 41, temperature descends gradually.Especially, first condenser 42 regulated making its temperature, such as high boiling point compositions such as DPC, and the gained phlegma is recycled in the water distilling apparatus 41 with condensation energetically with 80 ℃～150 ℃.Therefore, having through adjusting in 0～80 ℃ second and the follow-up condenser 42 of temperature, in first condenser 42, also there is not the uncondensed gas of liquefaction almost completely to liquefy.As required, the phlegma partial reflux that obtains by liquefaction is in water distilling apparatus 41, and remaining phlegma or whole phlegmas are discharged as overhead product.The installation of two or more condensers 42 has the following advantages.When even if a large amount of DPC discharges from distillation tower 41 as overhead product, this DPC can not take place to solidify and stop up in condenser 42 yet, this device is moved continuously, and can distill long-term and stably.The zero pour of DPC is 80 ℃, and this zero pour is higher than the zero pour (40 ℃) of PL.Therefore, when having a large amount of DPC in the condenser 42 of operation under the temperature condition that is being suitable for only making conventional low-boiling compound (for example PL) condensation, DPC might solidify in condenser 42.Therefore, two or more condensers 42 are set, behind condensation by force/removal high melting compound DPC, make the uncondensed gas condensation, this method can prevent to solidify effectively, and can stably keep the vacuum tightness in the water distilling apparatus 41.In addition,, except containing PL, also contain the boiling point a large amount of compounds lower, then it is desirable to use the such condenser of multistage 42 than PL if in the low-boiling point material that steams.
Then by explaining above-mentioned reflux with reference to figure 9.By using described reflux, when suppressing the evaporation of high boiling point composition, can improve and adopt distillation to carry out isolating efficient.
Adopt above-mentioned liquid-feeding pump 46 that the phlegma in the above-mentioned condensing tower is back in the water distilling apparatus 41, the horizontal component that is used for the return line 47 of this backflow is preferably had a down dip to liquid-feeding pump 46 side direction by water distilling apparatus 41 sides.It is desirable to, do not have the part of complete level or rising in the horizontal component of this inclination.Better is that its obliquity is a constant.In this kind situation, 2m place on the horizontal direction of pointing to liquid-feeding pump 46, downward-sloping amplitude it is desirable to be equal to or greater than 1cm, and that better is 5cm～1m.If have complete horizontal component or rising part, then owing to the difference of altitude that tilts to produce should be poor greater than the total height of rising part, the total height of rising part it is desirable to be equal to or less than 1m, and better is to be equal to or less than 10cm.Term " rising part " is meant opposite with the above sloping portion, is the part that is tilted to liquid-feeding pump 46 side direction by condenser 41 sides.
As shown in Figure 9, the part that tilts on the vertical or near normal ground that the part of horizontal component that tilts and the return line 47 between the liquid-feeding pump 46 can have, but this depends on the position of liquid-feeding pump 46.In this kind situation, leakage fluid dram 53 and 54 can be installed on the pipe section around the suction port of above-mentioned liquid-feeding pump 46 and the relief outlet, be trapped in before the liquid-feeding pump 46 and liquid afterwards so that discharge.
It is desirable to, above-mentioned return line 47 has following equipment, and this equipment is used to heat and its internal temperature is remained on the temperature of the fusing point that is not less than above-mentioned overhead product.In the situation that above-mentioned overhead product is grouped into by two or more one-tenth, it is desirable to, the inside of pipeline 47 can be heated and remained on the temperature of the fusing point that is not less than the material that wherein has peak melting point.When above-mentioned return line remained on the fusing point that is not less than above-mentioned overhead product, above-mentioned overhead product remained on liquid state or gaseous state and uncured, can further reduce overhead product in view of the above and stop up inner possibility.The example of this class heating/heat-preserving equipment comprises the equipment that wherein has double-sleeve structure or steam or electric flow channel structure.
It is desirable to, near on the part of distillation tower 41 supplying opening 55 is being set on this return line 47.In the situation that the operation of whole device stops, above-mentioned heating fluid imports by this supplying opening 55 and discharges by leakage fluid dram 54, cleans return line 47 in view of the above.In this kind situation, preferably between return line 47 and water distilling apparatus 41, valve 56 is set, flow in the water distilling apparatus 41 to prevent above-mentioned heating fluid.
Incidentally, aforesaid those are used for can be in order to reclaim PL or DPC as the isolated water distilling apparatus of overhead product with PL or DPC, for example in following steps, carry out the recovery of PL or DPC: the DPC distilation steps, wherein from DPC, remove impurity such as PL, to reclaim the DPC of purifying; Or PC polymerization procedure in the PC manufacturing step or PL distilation steps, wherein, Yi Bian be recovered in the by product PL (s-PL) that DPC and BPA reaction are produced, Yi Bian make PC by polymerization.This water distilling apparatus can be further used for separating in the step of PL or DPC as overhead product equally.
In addition, as mentioned above, the reflux of PL or DPC can be used for above-mentioned illustrative step though be used for refluxing, in these examples, the PL and the DPC that discharge from water distilling apparatus 41 as overhead product are returned in the water distilling apparatus 41, suppressing to be included in the PL that provided and the evaporation of the high boiling point composition among the DPC, and improve the efficient of fractionation by distillation in view of the above, but, in the step that above-mentioned reflux also can be used for need refluxing equally.Incidentally, can discharge above-mentioned high boiling point composition in addition by the bottom of water distilling apparatus 41.
Using these devices to make in the situation of DPC, in the part outside the horizontal component that return line 47 tilts, preferably has the relief outlet 57 that is used for discharging DPC from system.
By in these steps, using above-mentioned these devices respectively, when line clogging occurring, can easily eliminate this line clogging by purging method, in described purging method, provide heating fluid by the supplying opening 50 and 55 that is arranged on the related device.
＜embodiment 〉
[embodiment 1]
Below will handle the present invention will be explained in more detail with regard to s-PL.
(manufacturing of dehydration s-PL)
[PC polymerization procedure]
In nitrogen atmosphere, the BPA with 34.3kg/hr (kilogram/hour) supply (is made by Mitsubishi Chemical's (strain) in 130 ℃ of melting mixing; The BPA that in aftermentioned reference example 2, obtains) and with the DPC of 33.5kg/hr supply (make by Mitsubishi Chemical's (strain); The DPC that in aftermentioned reference example 1, obtains).By being heated to 130 ℃ raw material ingress pipe, with this mixture continuous charging in the first vertical stirring polymerization tank that is adjusted to normal pressure, nitrogen atmosphere and 210 ℃.Be installed in the aperture of the valve in the polymkeric substance vent line of the bottom that connects described groove by adjusting, make fluid level keep constant, thereby obtain 60 minutes average retention time.In addition, when described raw mix is begun to feed in raw material, with 0.5 * 10 -6The flow of mole/1 mole of BPA begins the cesium carbonate as catalyzer of aqueous solution form without interruption.The liquid polymeric reaction mixture that bottom land is discharged is fed in second, third and the 4th vertical polymerization tank and the 5th horizontal polymerizer in succession continuously subsequently.During reaction, regulate the fluid level in each groove, thereby obtain 60 minutes average retention time, simultaneously, steam the PL that produces as by product.Adopt multistage condenser condenses and liquefaction evaporation and expellant gas from first to the 3rd the polymerization tank respectively, partial condensation liquid is back to each polymerization tank, reclaim remaining phlegma and also be stored in the s-PL jar.On the other hand, adopting side by side two to freeze one of condenser solidifies evaporate expellant gas from the 4th and the 5th polymerizer.Freeze in the condenser by switching to another, fusing gained solid reclaims and is stored in the s-PL jar.
The polymerizing condition of each reactive tank is as follows: and first polymerization tank (210 ℃, 100Torr), second polymerization tank (240 ℃, 15Torr), the trimerization groove (260 ℃, 0.5Torr), the 4th polymerization tank (270 ℃, 0.5Torr).In addition, the speed of polycarbonate manufacturing is 38.3kg/hr.System's operation 400 hours.
The polymkeric substance that gained is in molten state imports twin screw extruder (Kobe Steel, Ltd (strain) manufacturing; Screw diameter, 0.046m; L/D=40.2), to wherein adding the butyl p-toluenesulfonate that accounts for polycarbonate 5ppm continuously.Butyl p-toluenesulfonate is for adopting agitator by stoste being dispersed in the master batch form that makes in the sheet polycarbonate, and utilizes the weight feeder to be fed to above-mentioned forcing machine in nitrogen atmosphere.Polymkeric substance is carried out granulation.The viscosity-average molecular weight of the polycarbonate that obtains (Mv) is 21000, and initial stage form and aspect (YI) are 1.7.
The mensuration of＜viscosity-average molecular weight (Mv) 〉
Under 20 ℃ temperature, adopt Ubbelohde viscometer, use the dichloromethane solution of PC concentration (C) to measure its specific viscosity (η sp) with 0.6g/dL (Grams Per Minute liter), adopt following two equatioies to calculate molecular weight by viscosity number:
ηsp/C＝[η](1+0.28ηsp)
[η]＝1.23×10 -4(Mv) 0.83
The mensuration of＜initial stage form and aspect (YI) 〉
In 120 ℃ of dry PC6 hours, and the J-100 injection moulding machine that adopts (strain) JSW to make was 360 ℃ of matrix that are injected into that are made into 3mm thickness in nitrogen atmosphere.The SC-1 that employing is made by Suga Test Instruments Co.Ltd. detects the YI value (the YI value is big more, and PC is painted serious more) of this sheet.
[s-PL purification step]
The s-PL that analysis is reclaimed by above-mentioned polymerization procedure with about 30.2kg/hr.The result detects the DPC of 5.0 weight %, the BPA of 0.5 weight %, the water of the oligopolymer of 0.3 weight % and 0.3 weight %.
This s-PL is by following two distillation tower continuous purifications.The one PL distillation tower is 2 operations at 200Torr and with reflux ratio, steams the water and the part PL that are comprised in view of the above together.Liquid at the bottom of the tower is transported to the 2nd PL distillation tower.The phenol that the low overhead product that boils of PL of being discharged by a PL distillation tower has the concentration of about 90 weight %.Subsequently, the 2nd PL distillation tower is 0.5 operation at 50Torr and with reflux ratio, obtains the s-PL of purifying with about 27kg/hr by the top.On the other hand, liquid PL mixture as tower at the bottom of liquid discharge with about 2.2kg/hr, liquid PL mixture contains DPC, BPA and the oligopolymer of 67 weight %, 7 weight % and 4 weight % respectively.
The manufacturing of (experimental example 1) DPC
At first, following method is explained in detail: will make DPC as the raw material of DPC from the dehydration s-PL that the 2nd PL distillation tower is as shown in Figure 5 discharged as overhead product, simultaneously, the low overhead product (D6) that boils of PC that is obtained by the s-PL of a PL distillation tower 30 dehydration is recycled to the DPC washing step.
[DPC reactions steps/desalination acid step]
Carry out the DPC manufacturing step according to schema shown in Figure 1.Incidentally, the DPC reactor 1 of use is made up of two placed in-line reactors.
To have the s-PL of purifying that 50 ℃ temperature is in molten state with 30.0kg/hr (0.32kmol/hr) continuous charging to DPC first reactor, add the PL that contains pyridine as catalyzer simultaneously, the described PL that contains pyridine obtains by the low boiling substance of being discharged as overhead product by aftermentioned low boiling substance distillation tower is dewatered.In so reinforced, the s-PL of above-mentioned purifying is heated to 150 ℃.Under fully stirring, with phosgene (CDC) gas with 3.56Nm 3/ hr (0.16kmol/hr) continuous charging is to DPC first reactor.Will be flow out and described reaction mixture with gas/liquid mixture phase is fed to DPC second reactor by upflow tube from DPC first reactor.Same by fully stirring, the content in adjusting DPC second reactor makes it have 150 ℃ temperature.Liquid reaction mixture is fed in the desalination acid tower 2.In desalination acid tower 2, utilize nitrogen to carry out counter current contact, so that the phenyl chloroformate and the PL complete reaction that form as intermediate at 160 ℃.The desalination acid solution body b of DPC with concentration of about 89 weight % is discharged continuously by the bottom of desalination acid tower 2.Almost 100% phosgene that is added is converted into DPC.On the other hand, the exhaust (D1 that DPC is synthesized gained; From the reaction exhaust of DPC second reactor with from the nitrogenous exhaust of desalination acid tower 2) mix, be cooled to 10 ℃ then.The gained phlegma is turned back to DPC second reactor, and the hydrogenchloride that obtains as uncooled gas then neutralizes and discharge with alkaline aqueous solution.
[DPC washing step/DPC water-washing step]
Gained desalination acid solution body b is delivered to tempering tank 3 with the recovery liquid d that contains DPC that reclaims from DPC recovery/distillation tower 8 described later.Then, this mixture is delivered in the alkali neutralizing well 4 with teflon liner.The aqueous sodium hydroxide solution of about 5 weight % (liquid that obtains by the low overhead product that boils of PC that mixes isolating water after 25 weight % aqueous sodium hydroxide solutions and the water wash step subsequently and obtain in above-mentioned s-PL purification step) is fed in the neutralizing well 4.This content mixed about 10 minutes at 80 ℃, then with pH regulator to 8.5.Standing separation is transferred to isolating organic phase in the washing bath 5.On the other hand, separate the remaining water (containing PL and salt) in back and contact, thereby contained PL almost all reclaims as the low overhead product that boils with water vapour.In next step, this overhead product is fed in the washing bath 5.In washing bath 5, use warm water washing organic phase with respect to organic 30 weight % that make an appointment.Water phase separated (being recycled to aforementioned neutralization/tempering tank) obtains the liquid f through washing, and this liquid is rough DPC (containing water, catalyzer pyridine and PL).
[DPC distilation steps/low boiling substance distilation steps]
Then, the above-mentioned stage casing that supplies to a DPC distillation tower 6 respectively with about 42kg/hr and 70mL/hr through the liquid f and the aqueous sodium hydroxide solution of 0.1N of washing.As a described DPC distillation tower 6, used have that theoretical plate number is 8, internal diameter is 150mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 1 the condition in the vacuum tightness of 20Torr, about 220 ℃ thermal medium oil temperature, 80 ℃～100 ℃ head temperature and reflux ratio, steam and contain the low-boiling material that has than DPC, promptly contain the mixed gas F of water, catalyzer pyridine and unreacted PL.After the mixed gas F dehydration, discharge section gas, and remaining gas is fed to aforementioned DPC first reactor.On the other hand, the first distillation leftover g that mainly contains DPC discharges at the bottom of by tower with about 37kg/hr.Water wherein is undetectable (being equal to or less than 10ppm).The content of pyridine and PL is respectively and can not detects (being equal to or less than 1ppm) and 50ppm.
[DPC distilation steps/high boiling material matter distilation steps]
In addition, these first distillation residue g supplies to the 2nd DPC distillation tower 7.As the 2nd DPC distillation tower 7, used have that theoretical plate number is 8, internal diameter is 200mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill overhead product ratio about 90% under 0.5 the condition in the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, about 180 ℃ head temperature and reflux ratio.As a result, by the DPC of top with about 33.5kg/hr acquisition purifying, and high boiling material matter DPC distillation leftover (X1) is discharged at the bottom of tower with about 4kg/hr.The DPC of described purifying is the high-purity product that contains the PL of 80ppm.
[DPC recovery/distilation steps]
In addition, the DPC distillation leftover (X1) of discharging from the bottom of high boiling material matter distillation tower is fed to DPC recovery/distillation tower 8 simultaneously, to carry out continuous still battery under following condition.Be recycled in the tempering tank 3 with the recovery liquid d that contains DPC that about 3.5kg/hr reclaims by the top, and discharge continuously with about 0.2kg/hr from liquid at the bottom of the tower of DPC recovery/distillation tower 8.For DPC recovery/distillatory condition, used that to have theoretical plate number be 8 continuous still battery tower, it has the internal diameter of 100mm and the height of 3.0m, reflux is equipped with on its top, its central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 0.5 the condition in the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, 180 ℃ head temperature and reflux ratio.After testing, in DPC recovery/distillation leftover (X1 ') (be from the tower of DPC recovery/distillation tower 8 at the bottom of liquid), the amount of the DPC derivative that DPC derivative that alkyl replaces and bromine replace is respectively about 7000ppm and about 800ppm by weight.
The manufacturing of (reference example 1) DPC
Make DPC in the mode identical with experimental example 1, difference is to use and is purchased the s-PL that PL (Mitsubishi Chemical's (strain) manufacturing) replaces purifying.
[result]
Through definite, when promptly box lunch uses s-PL, still obtain and use to be purchased the same yield of PL, and keep this manufacturing efficient.
The manufacturing of (comparative example 1) DPC
Make DPC in the mode identical, the purifying s-PL (water-content, 0.3 weight %) that difference has been to use the bypass by the PL distillation tower in the above-mentioned s-PL purification step to obtain with experimental example 1.As a result, because hydrolysis in the reactions steps of DPC, the DPC density loss among the desalination acid solution body b causes making the remarkable decline of efficient to 86 weight %.
The manufacturing of (reference example 2) BPA
(BPA manufacturing step)
Make BPA in the following manner according to the schema shown in Fig. 2～4.(commodity are called DIAION SK-104 with 60L sulfonic acid type acidic cation-exchange resin, Mitsubishi Chemical's (strain) makes) be filled in the flow type BPA reactor with thermoswitch, 15% sulfo group is neutralized by 4-pyridine ethane mercaptan in the described Zeo-karb.The liquid mixture that with the mol ratio of PL and acetone is 10: 1 imports in this BPA reactor and reaction at 80 ℃ of flow velocitys with 68.2kg/hr.The transformation efficiency of acetone is 80%.Low-boiling point material (unreacted acetone, water and part PL) is cooled to 50 ℃ with reaction mixture after discharging with the flow velocity of 5.1kg/hr, separates out the affixture crystallization.Filter this mixture, the crystallization of affixture is separated with mother liquor.Its flow velocity is respectively 16.5kg/hr and 46.5kg/hr.This mother liquor of 10 weight % is fed to the mother liquor treatment step, and remaining mother liquor circulates as the part of raw materials that imports the BPA reactor.
The affixture crystallization that so obtains is dissolved among the PL that supplies with the flow velocity of 27.2kg/hr again.Cooling gained solution to 50 ℃, to separate out crystallization, filtering separation mother liquor (32.5kg/hr) and affixture crystallization (11.3kg/hr) then.Under the decompression of 0.3mmHg, isolating crystallization is heated to 180 ℃, to remove PL.Therefore, obtaining flow velocity is the BPA that having of 7.7kg/hr is equal to or greater than 99.95% purity.
Handle the mother liquor that is fed in the above-mentioned mother liquor treatment step with PL vaporizer as shown in Figure 4, to steam part PL and to concentrate this mother liquor.Then, sodium hydroxide is added in the mother liquor, then its importing is adjusted to the bottom of residue reactor 14 of the temperature of the decompression of 50mmHg and 210 ℃ with the add-on of 0.1 weight %.(residence time 1hr), is discharged liquid at the bottom of the tower in the residue reactor 14 with the flow velocity of 0.5kg/hr from this system to keep the described reactor of operation under the constant condition in the fluid level that makes the bottom.In addition, mix overhead product and the PL that discharges from the top of residue reactor 14.Flow velocity with 4.2kg/hr imports this mixture the flow type regeneration reactor 15 that is filled with 4L sulfonic acid type acidic cation-exchange resin (commodity are called DIAION SK-104, and Mitsubishi Chemical's (strain) makes).This mixture reacts under 80 ℃ condition.The gained liquid reaction mixture is recycled to the BPA reactor that uses at initial period.
From reaction mixture, separate in the flow velocity importing PL recovery tower of low-boiling point material (unreacted acetone, water and part PL) that obtains with 5.1kg/hr.Meanwhile, by cat head supply ethylbenzene (azeotropic inhibition).As a result, the liquid mixture of acetone, water and ethylbenzene is discharged from the top of PL recovery tower with the flow velocity of 2.4kg/h, and PL discharges at the bottom of tower with the flow velocity of 3.5kg/h.In addition, the overhead product (acetone, water and ethylbenzene) of discharging from the top of PL recovery tower imports the acetone recovery tower.Acetone is discharged from the top of acetone recovery tower with the flow velocity of 0.7kg/h, and the mixture of water and ethylbenzene is discharged at the bottom of tower with the flow velocity of 1.6kg/h.The acetone that PL that bottom by the PL recovery tower obtains and the top by the acetone recovery tower obtain circulates as the part of raw materials that imports aforementioned synthesis reactor.
In addition, the PL of acetone and purifying adds in the aforementioned synthesis reactor, and the amount of adding is corresponding with the amount of amount of discharging from system and gained BPA.That is, the PL of acetone and purifying feeds in raw material with 2.9kg/h and 15kg/h respectively, to carry out the BPA building-up reactions continuously.Therefore, gained BPA imports in the above-mentioned PC polymerization procedure to make PC herein.
The PL of the purifying of above-mentioned use is purchased PL (water-content, 0.1 weight % by what handle industrial use; Impurity concentration, 0.05 weight %; Hydroxyacetone concentration, 20ppm) the PL that obtains, be that 175 ℃ and tower top pressure are the distillation tower distillation PL of 560mmHg at column bottom temperature then, with by recovered overhead PL, described processing is to make the described PL of being purchased be called the resin of DIAION SK-104H 80 ℃ of times that contact 50 minutes with Mitsubishi Chemical's (strain) manufacturers product.The content of the pyruvic alcohol among the PL of purifying is for being equal to or less than 1ppm.
The manufacturing of (experimental example 2) BPA
Next step, following method is made an explanation: will make BPA as the raw material of BPA from the dehydration s-PL that the 2nd PL distillation tower is as shown in Figure 5 discharged as overhead product, and will be recycled in the BPA/ water sepn step by the low overhead product (D6) that boils by the PC that the s-PL dehydration obtains.
The reaction mixture of mixing from above-mentioned BPA manufacturing step (reference example 2) separates the low-boiling point material (unreacted acetone, water and part PL) obtain (5.1kg/h) and the low overhead product that boils that obtains of the top of first distillation tower from above-mentioned s-PL purification step.This mixture is imported the PL recovery tower, meanwhile, by cat head supply ethylbenzene (azeotropic inhibition).As a result, the liquid mixture of acetone, water and ethylbenzene is discharged from the top of PL recovery tower with the flow velocity of 2.5kg/h, and PL discharges at the bottom of tower with the flow velocity of 4.0kg/h.In addition, the overhead product (acetone, water and ethylbenzene) that the top of PL recovery tower is discharged imports the acetone recovery tower.Acetone is discharged from the top of acetone recovery tower with the flow velocity of 0.7kg/h, and the mixture of water and ethylbenzene is discharged at the bottom of tower with the flow velocity of 1. kg/h.The acetone that PL that bottom by the PL recovery tower obtains and the top by the acetone recovery tower obtain circulates as the part of raw materials that imports aforementioned synthesis reactor.
In addition, acetone and PL are added in the BPA reactor, the amount of adding is corresponding with the amount of amount of discharging from system and gained BPA, and described PL is the s-PL by the purifying of the top acquisition of the 2nd PL distillation tower in the above-mentioned PL distilation steps.That is, acetone and this PL feed in raw material with 2.9kg/h and 14.5kg/h respectively, to carry out building-up reactions continuously.Therefore, the operation total system is with continuous manufacturing BPA.In addition, the BPA of gained is herein imported in the above-mentioned polymerization procedure to make PC.
As a result, be recycled in the BPA manufacturing step in the existing step by the low overhead product that boils that the top of first distillation tower in the s-PL purification step is obtained, nearly all PL that is included in the low overhead product that boils can be used as BPA and is reclaimed effectively with raw material.When carrying out above operation, make BPA and PC in the above described manner.As a result, gained BPA and PC are qualitatively without any problem.
The manufacturing of (comparative example 2) BPA
Make BPA in the mode identical with experimental example 2, difference is, uses the s-PL (water-content, 0.3 weight %) of the bypass acquisition by the PL distillation tower in the above-mentioned s-PL purification step to replace the s-PL of above-mentioned purifying.As a result, observe the decline of BPA yield.It is believed that its reason is that the water that comprises causes descending as the activity of the ion exchange resin of catalysts.
The manufacturing of (comparative example 3) BPA
Make BPA in the mode identical with reference example 2, difference is to use the PL that PL replaces the purifying in the reference example 2 that is purchased of industrial use.As a result, observe the decline of BPA yield.Through determining that the pyruvic alcohol that is comprised causes the decline of catalyst activity.
[embodiment 2]
Below adopt experimental example, the processing of the evaporation of the PC in PC polymerization procedure composition is handled 2 as s-PL make an explanation.
[DPC Production Example (1)]
Below show by being purchased the example that PL and CDC make DPC.
＜reactions steps 〉
When fused being purchased PL and pyridine catalyst and supplying in the reactor, under agitation phosgene is without interruption in 150 ℃.The byproduct hydrogen chloride gas of phosgenation reaction is cooled to 10 ℃.The gained phlegma is turned back in the reactor, and, discharge then with in the alkaline aqueous solution and uncooled gas.On the other hand, the liquid reaction mixture that contains about 91 weight %DPC is discharged continuously from reactor.The transformation efficiency of phosgene in reactions steps is almost 100%.
＜washing step 〉
The sodium hydroxide solution of liquid reaction mixture and about 5 weight % is fed in the neutralization/tempering tank with teflon liner.This content mixed about 10 minutes at 80 ℃, then with pH regulator to 8.5.After the neutralization,, and it is transferred in water washing/tempering tank by the standing separation organic phase.In water washing/tempering tank, to occupy the make an appointment warm water washing organic phase of 30 weight % of machine.Water phase separated obtains rough DPC (water that comprises 1 weight %, the pyridine of 2 weight %, the DPC of the PL of 8 weight % and 89 weight %).
＜low boiling substance distilation steps 〉
Then, described rough DPC is supplied to the stage casing of low boiling substance distillation tower with about 30kg/hr.As described low boiling substance distillation tower, used have that theoretical plate number is 8, internal diameter is 150mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 1 the condition in the vacuum tightness of 20Torr, about 220 ℃ thermal medium oil temperature, 80 ℃～100 ℃ head temperature, 160 ℃ midsection temperature and reflux ratio, steam and contain the boiling point material lower than DPC, that is, and water, pyridine and unreacted PL.(water is equal to or less than 10ppm by weight to discharge DPC continuously with about 26kg/hr at the bottom of the tower; Pyridine is equal to or less than 1ppm by weight; PL is 50ppm by weight).
＜high boiling material matter distilation steps 〉
In addition, described DPC (from liquid at the bottom of the tower of low boiling substance distillation tower) is supplied in the high boiling material matter distillation tower.As described high boiling material matter distillation tower, used have that theoretical plate number is 8, internal diameter is 200mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 0.5 the condition in the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, about 180 ℃ head temperature and reflux ratio.The result, obtain the DPC of purifying with about 23.5kg/hr from cat head, and discharging high boiling material matter (contain DPC derivative that the alkyl of about 350ppm by weight replaces and the DPC of the DPC derivative of the bromine replacement of about 40ppm) by weight at the bottom of the tower with about 2.5kg/hr, the DPC of described purifying contains the high-purity product of the PL of 80ppm by weight.
[DPC Production Example (2)]
Below show by being purchased PL and methylcarbonate and make the embodiment of DPC.
＜reactions steps 〉
To comprise and be purchased PL, methylcarbonate and (methylcarbonate is 390g/hr with the flow velocity of 600g/hr as the raw material liq of four phenoxide titaniums of catalyzer, PL is 200g/hr, four phenoxide titaniums are 0.5g/hr) be fed to the 10th column plate from the top of plate tower (the first reaction/distillation tower), described distillation tower number of actual plates is 50, and internal diameter is 50mm and highly is 5m.React/distill at the bottom of with mantle heater (mantle heater) heating tower.The methylcarbonate solution that contains methyl alcohol is discharged from cat head, is 12 to reflux with reflux ratio simultaneously.Contain at the bottom of the tower of gained carbonic acid aminomethyl phenyl ester liquid and a spot of DPC and discharge at the bottom of tower, and be fed to the 10th column plate from the top of plate tower (the second reaction/distillation tower), described distillation tower number of actual plates is 50, and internal diameter is 80mm and highly is 4m.In the second reaction/distillation tower, reaction is further carried out, and the liquid that contains gained DPC and carbonic acid aminomethyl phenyl ester is discharged at the bottom of tower.A large amount of unreacted methylcarbonates and the unreacted PL of part steam by the top of the second reaction/distillation tower, and are recycled in the first reaction/distillation tower.
＜circulation step 〉
To be fed to number of actual plates from the methylcarbonate solution that contains methyl alcohol that the first reaction/distillation tower is discharged and be 30 as overhead product, internal diameter is 32mm and highly is the distillation tower of 2.5m (azeotropic distillation column) stage casing.With reflux ratio is 5 to distill.Composition approaches the methyl alcohol of Azeotrope compositions and the liquid mixture of methylcarbonate is discharged by cat head, is fed to extraction/distillation tower then.In extraction/distillation tower, methyl alcohol separates with methylcarbonate.Methyl alcohol is discharged from system, and methylcarbonate then is recycled in the first reaction/distillation tower.From liquid at the bottom of the tower of aforementioned azeotropic distillation column is the methylcarbonate that contains a small amount of PL, and liquid at the bottom of this tower is recycled in the first reaction/distillation tower.
＜purification step 〉
To discharge from the bottom of the second reaction/distillation tower continuously and contain the high boiling reaction mixture importing vaporizer of catalyzer and DPC, the evaporation condensate that contains catalyzer be discharged by this vaporizer.On the other hand, the evaporation composition that contains a large amount of DPC that form in vaporizer is fed to the diphenyl carbonate purification column.Regulate purification column; Making its tower top pressure is that 20Torr and column bottom temperature are 190 ℃.The low mixture that boils that contains phenol and carbonic acid aminomethyl phenyl ester is discharged as overhead product by cat head.The described mixture of backflow part is recycled to the second reaction/distillation tower with remaining mixture.On the other hand, the height impurity that boils is discharged by the bottom of diphenyl carbonate purification column, and DPC obtains by midsection.
Carry out aforesaid operations continuously, be in plateau up to each step.Analyze to the diphenyl carbonate sampling and by high performance liquid chromatography.As a result, in the diphenyl carbonate of gained, detect the carbonic acid aminomethyl phenyl ester of 300ppm by weight.In PL, the yield of DPC is about 95%.
[BPA Production Example]
Below show by being purchased PL and acetone and make the example of BPA.
(commodity are called DIAION SK-104 with 60L sulfonic acid type acidic cation-exchange resin, Mitsubishi Chemical's (strain) makes) be filled in the flow type synthesis reactor with thermoswitch, 15% sulfo group is neutralized by 4-pyridine ethane mercaptan in the described exchange resin.The liquid mixture that with the mol ratio of PL and acetone is 10: 1 imports in this synthesis reactor and reaction at 80 ℃ of flow velocitys with 68.2kg/hr.The transformation efficiency of acetone is 80%.After low-boiling point material (unreacted acetone, water and part PL) is discharged with the flow velocity of 5.1kg/hr, reaction mixture is cooled to 50 ℃ and separate out the affixture crystallization.Filter this mixture, the crystallization of affixture is separated with mother liquor.Its flow velocity is respectively 16.5kg/hr and 46.5kg/hr.10 weight % of this mother liquor are fed to the mother liquor treatment step, and remaining mother liquor circulates as the part of raw materials that imports synthesis reactor.
The affixture crystallization that so obtains is dissolved among the PL that supplies with the flow velocity of 27.2kg/hr again.Cooling gained solution to 50 ℃ to separate out crystallization, filters then, will separate affixture crystallization (11.3kg/hr) from mother liquor (32.5kg/hr).Under the decompression of 0.3mmHg, isolating crystallization is heated to 180 ℃, to remove PL.Therefore, obtain to have the BPA that is equal to or greater than 99.95% purity with the flow velocity of 7.7kg/hr.
On the other hand, concentrate the mother liquor that is fed to the mother liquor treatment step by steaming part PL.Then, the sodium hydroxide of 0.1 weight % is added in the mother liquor, then it is imported the bottom of decomposition/distillation tower that has the temperature of the decompression of 50mmHg and 210 ℃ through adjusting.Keep operation described tower (residence time, 1 hour) under the constant condition in the fluid level that makes the bottom, from this system, discharge liquid at the bottom of the tower in the decomposition/distillation tower with the flow velocity of 0.5kg/hr.In addition, the overhead product and the aforementioned PL that will discharge from the top of decomposition/distillation tower mixes.Flow velocity with 4.2kg/hr imports this mixture the flow through reactors that is filled with 4L sulfonic acid type acidic cation-exchange resin (commodity are called DIAION SK-104, and Mitsubishi Chemical's (strain) makes).This mixture reacts under 80 ℃ condition.The gained liquid reaction mixture is recycled to the synthesis reactor of using at initial period.
To be purchased PL (18.5kg/hr) and acetone (3.6kg/hr) is added in the synthesis reactor, additional amount is corresponding with the amount of amount of discharging from system and gained dihydroxyphenyl propane.Therefore, carry out building-up reactions continuously, and the operation total system is with continuous manufacturing BPA.
[PC Production Example (1)]
In the example of following demonstration, make PC by the BPA of gained in the DPC of gained in the above-mentioned DPC Production Example (1) and the above-mentioned BPA Production Example by step shown in Figure 6.
＜PC polymerization procedure 〉
In nitrogen atmosphere, use tempering tank 21 with 0.977 weight ratio melting mixing DPC and BPA.In nitrogen atmosphere, with this mixture continuous charging in the first vertical stirring polymerization tank 22 of the pressure that has 210 ℃ temperature and 100Torr through adjusting.Place the aperture of valve of the polymkeric substance vent line of the bottom that connects described groove by adjusting, make fluid level keep constant, thereby obtain 60 minutes average retention time.In addition, when described raw mix is begun to feed in raw material, with 0.5 * 10 -6The flow of mole/1 mole of BPA begins the cesium carbonate as catalyzer of aqueous solution form without interruption.The liquid polymeric reaction mixture that bottom land is discharged is fed in the second vertical polymerization tank 23 and the 3rd vertical polymerization tank 24 and the 4th horizontal polymerizer 25 in succession continuously subsequently.During reaction, regulate the fluid level in each groove, thereby obtain 60 minutes average retention time, meanwhile, steam the PL that produces as by product.Adopt reflux 33a and 33b and multistage condenser 26 and 27 condensations and liquefaction from first polymerization tank 22 and second polymerization tank 23, to evaporate expellant gas respectively respectively.Each phlegma of part is back in each polymerization tank, reclaims remaining phlegma and be stored in a PC with among the PL withdrawing can 29a.The opposing party and, adopt side by side two to freeze one of condenser and solidify and from trimerization groove 24, evaporate expellant gas.Freeze in the condenser by switching to another, fusing gained solid reclaims and is stored in the 2nd PC with among the PL withdrawing can 29b.In this operation, the PC evaporation composition of discharging from first polymerization tank 22 and second polymerization tank 23 as overhead product all is stored in a PC with among the PL withdrawing can 29a, and all is stored in the 2nd PC with among the PL withdrawing can 29b as the PC evaporation composition that overhead product is discharged from trimerization groove 24.
The polymerizing condition of each polymerization tank is as follows: and first polymerization tank 22 (210 ℃, 100Torr), second polymerization tank 23 (240 ℃, 15Torr), trimerization groove 24 (260 ℃, 0.5Torr), the 4th polymerizer 25 (280 ℃, 0.5Torr).
The polymkeric substance that gained is in molten state imports twin screw extruder (Kobe Steel, Ltd (strain) manufacturing; Screw diameter, 0.046m; L/D=40.2), when wherein the relative polycarbonate of continuous interpolation is the butyl p-toluenesulfonate of 5ppm, carry out granulation.The PC that so obtains has 21000 viscosity-average molecular weight (Mv) and 1.7 initial stage form and aspect (YI).The method that is used for determining molecular weight (Mv) and initial stage form and aspect (YI) is carried out as stated above.
＜PC evaporates composition 〉
The amount and the composition of each PC evaporation composition that mensuration reclaims from above-mentioned polymerization procedure.The gained result is as follows.
The one PC PL withdrawing can 29a
Whole PL amounts that the amount of the phenol in the PC evaporation composition p1 that reclaims steams in respect to the PC polymerization procedure are about 60%.Except PL, also detect the DPC of 1.1 weight %.BPA and oligopolymer composition then do not detect.
The 2nd PC PL withdrawing can 29b
Whole PL amounts that the amount of the phenol in the 2nd PC evaporation composition p2 that reclaims steams in respect to the PC polymerization procedure are about 40%.Except PL, also detect the DPC of 6.0 weight %.And BPA and the detected amount of oligopolymer composition are respectively 1.2 weight % and 0.3 weight %.
[PC Production Example (2)]
In the example of following demonstration, make PC by the BPA that obtains in the DPC of above-mentioned DPC Production Example (2) gained and the above-mentioned BPA Production Example.
＜PC polymerization procedure 〉
Make PC in the mode identical with aforementioned PC Production Example (1), difference is that DPC with above-mentioned DPC Production Example (2) gained is as DPC.The Mv of gained PC be 21000 and initial stage YI be 1.7.It has the identical quality of PC with the middle gained of above-mentioned aromatic copolycarbonate Production Example (1).
＜PC evaporates composition 〉
The amount and the composition of each PC evaporation composition that mensuration reclaims from above-mentioned polymerization procedure.The gained result is as follows.
The one PC PL withdrawing can 29a
Whole PL amounts that the amount of phenol steams in respect to the PC polymerization procedure in the PC evaporation composition p1 that reclaims are about 60%.Except PL, also detect the DPC of 1.1 weight % and the methyl alcohol of 95 ppm by weight.BPA and oligopolymer composition then do not detect.
The 2nd PC PL withdrawing can 29b
Whole PL amounts that the amount of the phenol in the 2nd PC evaporation composition p2 that reclaims steams in respect to the PC polymerization procedure are about 40%.Except PL, also detect the DPC of 6.0 weight %.In addition, BPA and the detected amount of oligopolymer composition are respectively 1.2 weight % and 0.3 weight %.Do not detect methyl alcohol (being equal to or less than 5ppm by weight).
(experimental example 1)
The PC that obtains in above-mentioned PC Production Example (1) that use contains by-product phenol flashes to and assigns to make DPC and BPA.
The manufacturing of＜DPC 〉
Make DPC by carrying out the method identical with above-mentioned DPC Production Example (1), difference is, evaporates composition p1 with a PC who reclaims in the above-mentioned PC Production Example (1) and replaces 60% of the employed PL of being purchased in the aforementioned DPC Production Example (1).As a result, identical in the phosgene transformation efficiency in reactions steps and the quality of gained DPC and the DPC Production Example (1), and be gratifying.
The manufacturing of＜BPA 〉
Make BPA by carrying out the method identical with above-mentioned BPA Production Example, difference is, evaporates composition p2 with the 2nd PC that reclaims in the above-mentioned PC Production Example (1) and replaces adding continuously in the aforementioned BPA Production Example and be purchased 40% of PL in the synthesis reactor.As a result, the quality of the transformation efficiency of acetone and dihydroxyphenyl propane is gratifying.
(experimental example 2)
Use contains being flashed to by the PC of acquisition in the above-mentioned PC Production Example (2) of by-product phenol assigns to make DPC and BPA.
The manufacturing of＜DPC 〉
Make DPC by carrying out the method identical with above-mentioned DPC Production Example (2), difference is, evaporates composition p1 with a PC who reclaims in the above-mentioned PC Production Example (2) and replaces 60% of the employed PL of being purchased in the aforementioned DPC Production Example (2).The result can obtain the identical DPC of quality.Through determining, do not have problems even if enter in the system derived from the methyl alcohol of carbonic acid aminomethyl phenyl ester yet.
The manufacturing of＜BPA 〉
Make BPA by carrying out the method identical with above-mentioned BPA Production Example, difference is, evaporates composition p2 with the 2nd PC that reclaims in the above-mentioned PC Production Example (2) and replaces adding continuously in the aforementioned BPA Production Example and be purchased 40% of PL in the synthesis reactor.As a result, the quality of the transformation efficiency of acetone and dihydroxyphenyl propane is gratifying.In addition, do not detect methanol concentration at the raw material that is used for reacting.
(comparative experiments example 1)
Use the 2nd PC evaporation composition p2 that reclaims in the above-mentioned PC Production Example (1) to make DPC.
The manufacturing of＜DPC 〉
Make DPC by carrying out the method identical with above-mentioned DPC Production Example (1), difference is, with the 2nd PC evaporation composition p2 that reclaims in the above-mentioned PC Production Example (1) replace in the aforementioned DPC Production Example (1) employed all be purchased PL.The result has stopped up in order to the pipeline of transfer liquid reaction mixture to washing step, and this operation can not be proceeded.
(comparative experiments example 2)
Use the PC evaporation composition p1 that reclaims in the above-mentioned PC Production Example (2) to make BPA.
The manufacturing of＜BPA 〉
Make BPA continuously in the mode identical with above-mentioned BPA Production Example, difference is, replaces adding continuously in the aforementioned BPA Production Example whole PL that are purchased in the synthesis reactor with the PC evaporation composition p1 (containing the methyl alcohol of 95ppm by weight) that reclaims in the above-mentioned PC Production Example (2).As a result, the transformation efficiency of acetone significantly descends, and promptly drops to 55.0%.It is believed that contained methyl alcohol causes the decline of catalyst performance.When building-up reactions, because the circulating mother liquor dilution, the methanol concentration in the raw material phenol is about 30ppm by weight.
[embodiment 3]
Handle 3 as s-PL, below adopt experimental example, make an explanation according to the classification that impurity carried out with the method that is purchased PL utilizing PC evaporation composition p.
(experimental example 1)
(manufacturing of DPC)
＜reactions steps 〉
(Mitsubishi Chemical's (strain) makes fused being purchased PL; Cresols content is 45ppm by weight; Hydroxy acetone content is 27ppm by weight; Hereinafter referred to as " PL1 ") and the pyridine catalyst continuous charging in reactor time, under agitation in 150 ℃ with the phosgene continuous charging.To be cooled to 10 ℃ as the hydrogen chloride gas that by product produces by phosgenation reaction.The gained phlegma is turned back in the reactor, and, discharge then with in the alkaline aqueous solution and uncooled gas.On the other hand, the liquid reaction mixture that contains the 91 weight %DPC that have an appointment is discharged continuously by reactor.
＜washing step 〉
The aqueous sodium hydroxide solution of aforesaid liquid reaction mixture and about 5 weight % is fed in the neutralization/tempering tank with teflon liner.This content mixed about 10 minutes at 80 ℃, then with pH regulator to 8.5.After the neutralization,, and it is transferred in water washing/tempering tank by the standing separation organic phase.In water washing/tempering tank, use warm water washing organic phase with respect to organic 30 weight % that make an appointment.Water phase separated obtains rough DPC (water that comprises 1 weight %, the pyridine of 2 weight %, the DPC of the PL of 8 weight % and 89 weight %).
＜low boiling substance distilation steps 〉
Then, described rough DPC is supplied to the stage casing of low boiling substance distillation tower with about 30kg/hr.As this low boiling substance distillation tower, used have that theoretical plate number is 8, internal diameter is 150mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 1 the condition in the vacuum tightness of 20Torr, about 220 ℃ thermal medium oil temperature, 80 ℃～100 ℃ head temperature, 160 ℃ midsection temperature and reflux ratio, steam and contain the boiling point material lower than DPC, that is, and water, pyridine and PL.(water is equal to or less than 10ppm by weight to discharge DPC continuously with about 26kg/hr at the bottom of the tower; Pyridine is equal to or less than 1ppm by weight; PL is 50ppm by weight; )
＜high boiling material matter distilation steps 〉
In addition, described DPC (from liquid at the bottom of the tower of low boiling substance distillation tower) supplies in the high boiling material matter distillation tower.As described high boiling material matter distillation tower, used have that theoretical plate number is 8, internal diameter is 200mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 0.5 the condition in the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, about 180 ℃ head temperature and reflux ratio.As a result, obtain the DPC (containing the PL of about 80ppm by weight) of purifying with about 23.5kg/hr by the top.
(reference example 1)
Make DPC in the mode identical with experimental example 1, difference is to use following phenol to replace the above-mentioned PL that is purchased (PL1).Described phenol is that (cresols content is 5ppm to the by-product phenol that obtains by distillation/purifying under the following conditions of the PC evaporation composition p that obtains in the PC manufactory of Mitsubishi Chemical's (strain) by weight; Hydroxy acetone content is by weight for being equal to or less than 1ppm; Hereinafter referred to as " PL2 ").
[distillation/purification condition]
In first distillation tower, be 2 to steam water and the part PL that is comprised with reflux ratio at 200Torr.Liquid at the bottom of the gained tower is supplied in the second column.In second column, be 0.5 by-product phenol with reflux ratio from cat head acquisition purifying by 50Torr.The liquid PL mixture that comprises high boiling point composition (that is, DPC, BPA and oligopolymer) as tower at the bottom of liquid and discharging continuously.
[result]
Promptly box lunch will be not purified is purchased PL and is used for DPC and makes, and also obtains identical with the by-product phenol that the uses process distillation/purifying not DPC of high purity such as variable color of high purity that has.
The manufacturing of (experimental example 2 and comparative example 1) BPA
((commodity are called DIAION SK-104H to the sulfonated bodies of vinylbenzene/divinyl benzene crosslinked multipolymer with the sulfonic acid type acidic cation-exchange resin, Mitsubishi Chemical's (strain) makes)) be filled in the reactor, the sulfo group of 15 weight % is carried out modification by 4-(2-mercaptoethyl) pyridine in the described exchange resin.Material flow (the PL: acetone=13: 1 (in mole)) pass through reactor continuously that will form by above-mentioned PL (PL2 or PL1) and acetone (Mitsubishi Chemical's (strain) manufacturing), with the wetting catalyzer of phenol is benchmark, the LHSV of this material flow (liquid hourly space velocity) is 5/hr, carries out the BPA formation reaction 1008 hours under 70 ℃ temperature.Table 1 has shown the acetone conversion of reaction beginning mensuration in the time of back 120 hours, the acetone conversion that the reaction beginning is measured in the time of back 1008 hours, and the selection rate of BPA.In addition, the likening of measuring in the time of back 120 hours with the acetone conversion and the beginning of reaction beginning mensuration in the time of back 1008 hours to of acetone conversion is active sustainment rate.Calculation result is also shown in the table 1.
Phenol Transformation efficiency (%) Active sustainment rate (%)
After 120 hours After 1008 hours
Experimental example 2 PL2 73.8 70.8 94.7
Comparative example 1 PL1 78.5 58.6 74.6
Incidentally, transformation efficiency (%) and activity of such catalysts sustainment rate (%) adopt following equation to calculate.
Transformation efficiency (%)={ [(acetone feeding quantity)-(unreacted amounts of acetone)]/(acetone feeding quantity) } * 100
Active sustainment rate (%)=[(acetone conversions after 1008 hours)/(acetone conversions after 120 hours)] * 100
[result]
When using the PL that obtains from the PL overhead product of polymerization procedure by distillation/purifying, can obtain being different from use and be purchased the high transformation efficiency of situation of PL and high catalyst activity sustainment rate.
In addition, use the PL that obtains from the PL overhead product of polymerization procedure by distillation/purifying to obtain the BPA of white tone, use is purchased PL and has then obtained yellowish BPA.Can expect, in the PC manufacturing step, use these BPA products will obtain following result.In the situation of using the PL manufacturing BPA that obtains from the PL overhead product of polymerization procedure by distillation/purifying, it is believed that the highly purified white PC of acquisition.On the contrary, when use is purchased PL manufacturing BPA, it is believed that to obtain little yellow and the lower PC of purity.
[embodiment 4]
Next step below will explain the present invention with regard to the connection between manufacturing step in more detail according to schema shown in Figure 7.What be different from Fig. 7 is that BPA stores step and places heating/fusion step (step (d)) and PL to remove between the step (step (e)).
(experimental example 1)
[manufacturing of BPA]
(commodity are called DIAION SK-104 with 60L sulfonic acid type acidic cation-exchange resin, Mitsubishi Chemical's (strain) makes) be filled in the flow type BPA reactor with thermoswitch, 15% sulfo group is neutralized by 4-pyridine ethane mercaptan in the described exchange resin.The liquid mixture that with the mol ratio of PL and acetone (A) is 10: 1 imports in this synthesis reactor and reaction at 80 ℃ of flow velocitys with 68.2kg/hr.The transformation efficiency of acetone (A) is 80%.After low-boiling point material (unreacted acetone, water and part PL) is discharged with the flow velocity of 5.1kg/hr, reaction mixture is cooled to 50 ℃ and separate out the affixture crystallization.Filter this mixture, the affixture crystallization is separated with mother liquor.Its flow velocity is respectively 16.5kg/hr and 46.5kg/hr.10 weight % of this mother liquor are fed to the mother liquor treatment step, and remaining mother liquor circulates as the part of raw materials that imports synthesis reactor.
The affixture crystallization that so obtains is dissolved in the phenol of supplying with the flow velocity of 27.2kg/hr again.Cooling gained solution to 50 ℃ to separate out crystallization, filters then, and mother liquor (32.5kg/hr) is separated with affixture crystallization (11.3kg/hr).Isolating crystallization is mixed with PL with the purifying of 1.5kg/hr supply, with the mixture of the PL of the BPA for preparing 60 weight % and 40 weight %.With 12.8kg/hr this mixture is imported BPA hold tank (following condition) and storage therein, and the PL that supplies to subsequently with 12.0kg/hr removes in the step.
Employed BPA hold tank is made by SUS304, has the capacity (the Vb/Fb value of wherein stipulating in specification sheets is 22) of 150L.Internal system seals with nitrogen, and the internal temperature of BPA/PL mixture is adjusted to 120 ℃.In addition, in the BPA/PL mixture, after testing, it is believed that the PL-sulfonic acid that derives from ion exchange resin is about 10ppb by weight.Therefore, before this mixture is transferred to hold tank, add the caustic soda aqueous solution of the described acid substance aequum that neutralizes fully, with its neutralization to this mixture.During the operation beginning, the fluid level in the hold tank begins to rise rallentando.
Subsequently, the BPA/PL mixture in the BPA hold tank is transferred in the PL removal step continuously with 12.0kg/hr.Under the decompression of 0.3mmHg with this mixture heating up to 180 ℃, to remove PL.Therefore, be that to have obtained purity be 99.95% BPA for 7.2kg/hr (6.8L/hr) with the flow velocity.Gained BPA is itself to supply to the aromatic copolycarbonate manufacturing step that will be described below.
On the other hand, handle the mother liquor that is fed to mother liquor treatment step (not shown in Figure 7, as to see Fig. 4), to steam part PL and to concentrate this mother liquor with PL vaporizer 13.Then, the sodium hydroxide of 0.1 weight % is added in the mother liquor, then it is imported the bottom of residue reactor 14 that has the temperature of the decompression of 50mmHg and 210 ℃ through adjusting.Keep operation described reactor (residence time, 1 hour) under the constant condition in the fluid level that makes the bottom, from this system, discharge liquid at the bottom of the tower in the residue reactor 14 with the flow velocity of 0.5kg/hr.In addition, overhead product and PL that the top of residue reactor 14 is discharged mix, and this mixture is imported in the flow type revivifier 15 that is filled with 4L sulfonic acid type acidic cation-exchange resin (commodity be called DIAION SK-104, Mitsubishi Chemical's (strain) manufacturing) with the flow velocity of 4.2kg/hr.This mixture reacts under 80 ℃ condition.The gained liquid reaction mixture is recycled to the BPA reactor that uses at initial period.
Be purchased PL (18.5kg/hr) and acetone (3.6kg/hr) and add in the aforementioned BPA reactor, additional amount is corresponding with the amount of amount of discharging from system and gained BPA.Therefore, carry out building-up reactions continuously, and operational system and make BPA continuously.
[PC manufacturing]
The example that below shows the schema manufacturing PC that shows according to Fig. 5.
In nitrogen atmosphere, by tempering tank 21 with 1.024 weight ratio melting mixing DPC and BPA.In nitrogen atmosphere, with this mixture continuous charging in the first vertical stirring polymerization tank 22 of the pressure that has 210 ℃ temperature and 100Torr through adjusting.Place the aperture of valve of the polymkeric substance vent line of the bottom that is connected to described groove by adjusting, make fluid level keep constant, thereby obtain 60 minutes average retention time.In addition, when described raw mix is begun to feed in raw material, with aqueous solution form as the cesium carbonate of catalyzer with 0.5 * 10 -6The flow velocity of mole/1 mole of BPA begins without interruption.The liquid polymeric reaction mixture that bottom land is discharged is fed in the second vertical polymerization tank 23 and the 3rd vertical polymerization tank 24 and the 4th horizontal polymerization tank 25 in succession continuously subsequently.During reaction, regulate the fluid level in each groove, thereby obtain 60 minutes average retention time, meanwhile, steam the PL that produces as by product.The PC evaporation composition p that adopts corresponding multistage condenser condenses and liquefaction to discharge from first polymerization tank and second polymerization tank is back to the part of phlegma separately in each polymerization tank, reclaims remaining phlegma and also is stored in PC with in the PL withdrawing can 29.On the other hand, adopting side by side two to freeze one of condenser solidifies by evaporation and forms and each expellant gas in trimerization groove 24 and the 4th polymerization tank 25.Freeze in the condenser by switching to another, fusing gained solid reclaims and is stored in PC with in PL withdrawing can 29 (not shown).
The polymerizing condition of each polymerization tank is as follows: and first polymerization tank (210 ℃, 100Torr), second polymerization tank (240 ℃, 15Torr), the trimerization groove (260 ℃, 0.5Torr), the 4th polymerizer (280 ℃, 0.5Torr).
The polymkeric substance that gained is in molten state carries out granulation, simultaneously to adding butyl p-toluenesulfonate continuously by the amount of 5ppm by weight for PC.The Mv of the carbonic ether that so obtains be 21000 and initial stage YI be 1.8.
The mensuration of＜molecular weight (Mv) 〉
Under 20 ℃ temperature, adopt Ubbelohde viscometer, use the dichloromethane solution of PC concentration (C) to measure its specific viscosity (η sp) with 0.6g/dL (Grams Per Minute liter), adopt following two equatioies to calculate molecular weight (Mv) by viscosity number:
ηsp/C＝[η](1+0.28ηsp)
[η]＝1.23×10 -4(Mv) 0.83
The mensuration of＜initial stage form and aspect (YI) 〉
In 120 ℃ of dry PC6 hours, and the J-100 injection moulding machine that adopts (strain) JSW (strain) to make was 360 ℃ of matrix that are injected into that are made into 3mm thickness in nitrogen atmosphere.The SC-1 that employing is made by Suga Test Instruments Co.Ltd. detects the YI value (the YI value is big more, and PC is painted serious more) of this sheet.
Aforesaid operations continues a week.After this, for cleaning the purpose of BPA crystallizer, stopped building-up reactions/crystallisation step about 8 hours temporarily.But during this, use the liquid mixture that is stored in the hold tank to move subsequent step continuously whole, can make BPA and aromatic copolycarbonate thus.Identical with the initial stage quality at these products of continuous operation one all gained with quality at the product of the acquisition in service subsequently of subsequent step, and be gratifying.
(experimental example 2)
Make BPA and aromatic copolycarbonate continuously by carrying out the method identical with experimental example 1, difference is that the capacity of BPA hold tank was changed into 2m during the BPA of above-mentioned experimental example 1 made 3(Vb/Fb=294).The Mv of gained polycarbonate be 21000 and initial stage YI be 1.8.
This operation continues 2 months.During this, aromatic copolycarbonate demonstrates 1.8～1.9 form and aspect (initial stage YI), and products therefrom is gratifying whole.Stopped BPA building-up reactions/crystallisation step about 3 days temporarily.But use the liquid mixture that is stored in the hold tank can move subsequent step continuously, the quality of the product that so obtains is gratifying.After this, carried out once 3 days interval by a definite date as mentioned above at per 2 months, intermittently move the prior step (step before BPA hold tank) of BPA in making, and adopt aforesaid way to move BPA continuously and make later steps in making to aromatic copolycarbonate.Therefore, in the time of about half a year, obtain the gratifying aromatic copolycarbonate of quality continuously.
(comparative experiments example 1)
Make BPA and aromatic copolycarbonate continuously by carrying out the method identical with experimental example 1, difference is that the capacity of BPA hold tank was changed into 50L (Vb/Fb=7) during the BPA of above-mentioned experimental example 1 made.The Mv of gained polycarbonate be 21000 and initial stage YI be 1.8.
Yet after self-operating had begun past 2 days, it is full that the BPA hold tank becomes, and this has reduced the manufacturing speed of the prior step (step before the hold tank) in the BPA manufacturing.Therefore regulate operation to keep the constant of fluid level in the hold tank.After this, only stop prior step.As a result, the fluid level in the hold tank descends rapidly, and this jar became empty in about 4 hours, need stop subsequent step and all PC steps.
(comparative experiments example 2)
In comparative experiments example 1, make continuously BPA, wherein regulate the manufacturing speed of the prior step (step before hold tank) of BPA in making, to keep the constant of fluid level in the hold tank.The BPA of cooling gained, granulation then, and with BPA powder hopper (capacity, the 1m of these particle interim storages in new installation 3) in.After this, when being fed to and being dissolved in described particle in the DPC solution, make PC in the above described manner continuously with the powder weight feeder.As long as have BPA in the powder hopper, stop the BPA step PC manufacturing speed is not had problems temporarily.But from the viewpoint of thermo-efficiency, this method is disadvantageous, and this is because interim cooling fused BPA is being translated into powder, and need heat when dissolving thereafter.In addition, can produce dust when supply BPA, this can cause the gas tube blocking problem.
(comparative experiments example 3)
In comparative experiments example 1, make BPA continuously, wherein accelerate the manufacturing speed of the step after the hold tank a little, to keep the constant of fluid level in the hold tank with 7.7kg/hr.The capacity that the pure BPA of gained is stored in new installation is 2m 3The jar in, wherein internal temperature is adjusted to 160 ℃.After this, identical with comparative experiments example 1, it is reinforced with 7.2kg/hr that BPA is made raw material as PC.The initial stage YI of gained PC is 1.8.But along with the continuation of operation, form and aspect begin obvious deterioration.The remarkable deterioration of quality will be caused after the pure BPA fusion preservation.
(experimental example 3)
Below provided experimental example, wherein, BPA manufacturing step, DPC manufacturing step and PC manufacturing step have been interconnected, and BPA, DPC and PC storage step are included in these manufacturing steps.
[manufacturing of BPA]
Carrying out BPA in the mode identical with above-mentioned experimental example 1 makes.
[DPC manufacturing]
＜reactions steps 〉
With 6.4kg/hr be with temperature 50 ℃ fusion phenol with as the phenol continuous charging that contains pyridine of catalyzer in first reactor, the described phenol that contains pyridine obtains by the low-boiling point material of discharging from aftermentioned low boiling substance distillation tower as overhead product is dewatered.In so reinforced, fusion phenol is heated to 150 ℃.Under fully stirring, with 0.75Nm 3/ hr with phosgene gas continuous charging in first reactor.To flow out and described reaction mixture with gas/liquid mixture phase is fed to second reactor from first reactor by upflow tube.Under fully stirring, also the content in second reactor is adjusted to 150 ℃ temperature.Liquid reaction mixture is fed in the degassing tower.In degassing tower, utilize nitrogen to carry out counter current contact, so that the phenyl chloroformate and the phenol complete reaction that form as intermediate at 160 ℃.The liquid reaction mixture of diphenyl carbonate with concentration of about 89 weight % is discharged continuously by the bottom of degassing tower.Almost 100% phosgene that is added is converted into diphenyl carbonate.On the other hand, will mix, be cooled to 10 ℃ then by the exhaust of the synthetic gained of diphenyl carbonate (from the reaction exhaust of second reactor with from the nitrogenous exhaust of degassing tower).The gained phlegma is turned back to second reactor, and the hydrogenchloride that obtains as uncondensed gas then neutralizes and discharge with alkaline aqueous solution.
＜washing step 〉
Diphenyl carbonate that reclaims with the gained liquid reaction mixture, from aftermentioned recovery/distillation tower and the aqueous sodium hydroxide solution of about 5 weight % (liquid that isolating water obtains after aqueous sodium hydroxide solution by mixing 25 weight % and the water wash step subsequently) are fed to respectively the neutralization/tempering tank with teflon liner.This content mixed about 10 minutes at 80 ℃, then with pH regulator to 8.5.After the neutralization, after leaving standstill, separate organic phase, and organic phase is transferred in water washing/tempering tank.On the other hand, separate the remaining water (containing PL and salt) in back and contact with water vapour, gained PL almost all reclaims as the water that contains phenol.In next step, described water is fed in water washing/tempering tank.In water washing/tempering tank, use the warm water washing organic phase of about 30 weight % with respect to organic phase.Water phase separated (being recycled to aforementioned neutralization/tempering tank) obtains rough diphenyl carbonate (containing water, catalyzer pyridine and phenol).
＜low boiling substance distilation steps 〉
Then, the aqueous sodium hydroxide solution of described rough diphenyl carbonate and 0.1N is supplied to the stage casing of low boiling substance distillation tower respectively with the flow velocity of about 9kg/hr and 15ml/hr.As this low boiling substance distillation tower, used have that theoretical plate number is 8, internal diameter is 100mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 1 the condition in the vacuum tightness of 20Torr, about 220 ℃ thermal medium oil temperature, 80 ℃～100 ℃ head temperature and reflux ratio, steam and contain the boiling point material lower than diphenyl carbonate, that is, and water, pyridine and unreacted phenol.After the low-boiling point material processed, these materials of discharge section, remaining material then are fed in first reactor of aforementioned lights gasification.On the other hand, at the bottom of tower, discharge diphenyl carbonate with about 7.8kg/hr.Water does not wherein detect (being equal to or less than 10ppm), and the content of pyridine and phenol is not respectively and detects (being equal to or less than 1ppm) and 50ppm.
＜high boiling material matter distilation steps 〉
In addition, described diphenyl carbonate (from liquid at the bottom of the tower of low boiling substance distillation tower) supplies in the high boiling material matter distillation tower.As described high boiling material matter distillation tower, used have that theoretical plate number is 8, internal diameter is 100mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.In the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, about 180 ℃ head temperature and reflux ratio is 0.5, and the ratio of overhead product is about under 90% the condition and distills.As a result, obtain the diphenyl carbonate of purifying from the top with about 7.1kg/hr (7L/hr), and at the bottom of tower, discharge high boiling material matter with about 0.8kg/hr.The diphenyl carbonate of described purifying is the high-purity product that contains the phenol of 80ppm.The described diphenyl carbonate of a certain amount of (about 100L) is stored in by SUS316 in 100 ℃ makes in the jar that capacity is 200L (the Vd/Fd value in the specification sheets regulation is 29), feed in raw material with 7L/hr as PC manufacturing raw material then.
＜recovery/distilation steps 〉
In addition, liquid is fed to recovery/distillation tower simultaneously at the bottom of the tower of discharging from the bottom of high boiling material matter distillation tower, with continuous still battery under following condition.Reclaim diphenyl carbonate by the top with about 0.7kg/hr, be recycled in neutralization/tempering tank, liquid is then discharged continuously with about 0.04kg/hr at the bottom of the tower.For diphenyl carbonate recovery/distillatory condition, used that to have theoretical plate number be 8 continuous still battery tower, it has the internal diameter of 50mm and the height of 3.0m, reflux is equipped with on its top, its central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 0.5 the condition in the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, 180 ℃ head temperature and reflux ratio.After testing, in liquid at the bottom of the tower of recovery/distillation tower, the amount of the dipheryl carbonate ester derivative that dipheryl carbonate ester derivative that alkyl replaces and bromine replace is respectively about 7000ppm and about 800ppm by weight.
[manufacturing of PC]
＜polymerization procedure 〉
In nitrogen atmosphere, in 130 ℃ of melting mixing with the dihydroxyphenyl propane of the above-mentioned acquisition of 7.2kg/hr supply with the diphenyl carbonate of 7.1kg/hr supply.By being heated to 130 ℃ raw material ingress pipe, with this mixture continuous charging in being adjusted in the normal pressure nitrogen atmosphere, having in 210 ℃ the first vertical stirring polymerization tank of temperature.Be installed in the aperture of the valve in the polymkeric substance vent line of the bottom that is connected to described groove by adjusting, make fluid level keep constant, thereby obtain 60 minutes average retention time.In addition, when described raw mix is begun to feed in raw material, with aqueous solution form as the cesium carbonate of catalyzer with 0.5 * 10 -6The flow velocity of mole/1 mole of dihydroxyphenyl propane begins without interruption.The liquid polymeric reaction mixture that bottom land is discharged is fed in second, third and the 4th vertical polymerization tank and the 5th horizontal polymerization tank in succession continuously subsequently.During reaction, regulate the fluid level in each groove, thereby obtain 60 minutes average retention time, meanwhile, steam the phenol that produces as by product.Adopt multistage condenser condenses and liquefaction to form and expellant gas from first to the 3rd the polymerization tank respectively separately, partial condensation liquid is back to polymerization tank, reclaim remaining phlegma and also be stored in the by-product phenol jar by evaporation.On the other hand, adopt side by side two to freeze the curing of one of condenser by evaporation formation and each expellant gas in the 4th and the 5th polymerization tank.Freeze in the condenser by switching to another, fusing gained solid reclaims and is stored in the above-mentioned by-product phenol jar.
The polymerizing condition of each reactive tank is as follows: and second polymerization tank (210 ℃, 100Torr), the trimerization groove (240 ℃, 15Torr), the 4th polymerization tank (260 ℃, 0.5Torr), the 5th polymerization tank (270 ℃, 0.5Torr).System is the 8.0kg/hr operation in the speed of polycarbonate manufacturing.
Then, the polymkeric substance that gained is in molten state imports twin screw extruder (Kobe Steel, Ltd (strain) manufacturing), being that the amount of 5ppm is to wherein adding butyl p-toluenesulfonate continuously with respect to polycarbonate.Butyl p-toluenesulfonate is for adopting agitator by stoste being dispersed in the master batch form that makes in the sheet polycarbonate, and utilizes the weight feeder to be fed to above-mentioned forcing machine in nitrogen atmosphere.Polymkeric substance is carried out granulation.The Mv of the polycarbonate that so obtains be 21000 and initial stage YI be 1.7.Molecular weight (Mv):
Under 20 ℃ temperature, adopt Ubbelohde viscometer, use the dichloromethane solution of polycarbonate concentration (C) to measure its specific viscosity (η sp) with 0.6g/dL, adopt following two equatioies to calculate molecular weight by viscosity number:
ηsp/C＝[η](1+0.28ηsp)
[η]＝1.23×10 -4(Mv) 0.83
Initial stage form and aspect (YI):
In 120 ℃ of dry polycarbonate resins 6 hours, and the J-100 injection moulding machine that adopts (strain) JSW to make was 360 ℃ of matrix that are injected into that are made into 3mm thickness in nitrogen atmosphere.The SC-1 that employing is made by Suga Test Instruments Co.Ltd. detects the YI value (the YI value is big more, and PC is painted serious more) of this sheet.
＜by-product phenol purification step 〉
The by-product phenol that is reclaimed by polymerization procedure with about 6.3kg/hr (6L/hr) of a certain amount of (about 100L) is stored in the by-product phenol jar (to be made by SUS304, has the capacity of 200L; The Vc/Fc that stipulates in the specification sheets is 33) in, carry out following distillation/purifying then.The phenol of gained purifying is made raw material as DPC and is circulated.An exposed part is replenished by being purchased PL.
First distillation tower is 2 operations at 200Torr with reflux ratio, in view of the above the water that is comprised is steamed with part phenol.Liquid at the bottom of the tower is transported to second column.Second column is 0.5 operation at 50Torr and reflux ratio, to obtain the phenol of purifying with about 5.8kg/hr by the top.The phenol of described purifying is fed to the DPC manufacturing step by the phenol purification groove.On the other hand, the liquid phenol mixture that contains the diphenyl carbonate, dihydroxyphenyl propane and the oligopolymer that are respectively 67 weight %, 7 weight % and 4 weight % as tower at the bottom of liquid discharge continuously.
Above-mentioned Therapy lasted was carried out 400 hours.In experimentation, because problems such as relevant temperature control need stop the DPC manufacturing step temporarily.But,, therefore do not need to stop total system, the measure that can take to solve described problem rapidly owing to used the liquid that is stored in the hold tank.At run duration, having produced Mv is 15000 grades of other polycarbonate, and this causes from the running modification of the composition of the by-product phenol of polymerization tank recovery.But, can in hold tank, reduce described variation, and can change the operational condition of by-product phenol purification step subsequently smoothly.
[embodiment 5]
Next step, the present invention will explain in more detail with regard to liquid waste disposal.Incidentally, the mensuration of viscosity-average molecular weight (Mv) and initial stage form and aspect (YI) has adopted method mentioned above.
(experimental example 1)
(DPC manufacturing step)
Carry out the DPC manufacturing step according to schema shown in Figure 1.Details is as follows.
[DPC reactions steps]
With when fusion PL and pyridine catalyst continuous charging are in DPC reactor 1, under agitation in 150 ℃ with phosgene (CDC) to continuous charging wherein.Then, mixture is delivered in the desalination acid tower 2.To be cooled to 10 ℃ as the hydrogen chloride gas (D1) that the phosgenation reaction by product produces.The gained phlegma is turned back in the reactor, use in the alkaline aqueous solution and remaining uncooled gas, discharge then.On the other hand, the desalination acid solution body that contains about 91 weight %DPC is discharged continuously by desalination acid tower 2.
[DPC washing step/DPC water-washing step]
B delivers in the tempering tank 3 with desalination acid solution body, delivers to then in the alkali neutralizing well 4 with teflon liner.In addition, the aqueous sodium hydroxide solution with about 5 weight % is fed in the alkali neutralizing well 4.This content mixed about 10 minutes at 80 ℃, then with pH regulator to 8.5.After the neutralization, after leaving standstill, separate organic phase and it is transferred in the washing bath 5.In washing bath 5, use warm water washing organic phase with respect to organic 30 weight % that make an appointment.Water phase separated obtains the liquid f through washing, and this liquid is rough DPC (water that comprises 1 weight %, the pyridine of 2 weight %, the DPC of the PL of 8 weight % and 89 weight %).
[DPC distilation steps/low boiling substance distilation steps]
Then, supply to the stage casing of a PL distillation tower 6 with about 30kg/hr through the liquid f of washing.As a described PL distillation tower 6, used have that theoretical plate number is 8, internal diameter is 150mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.In the vacuum tightness of 20Torr, about 220 ℃ thermal medium oil temperature, 80 ℃～100 ℃ head temperature, midsection temperature is that 160 ℃ and reflux ratio are to distill under 1 the condition, steam the mixed gas F that contains the boiling point material lower (that is, water, catalyzer pyridine and unreacted PL) than DPC.Discharge the first distillation leftover g at the bottom of the tower continuously with about 26kg/hr, described residue g be contain the tower of DPC at the bottom of liquid (water is equal to or less than 10ppm by weight; Pyridine is equal to or less than 1ppm by weight; PL is 50ppm by weight).
[DPC distilation steps/high boiling material matter distilation steps]
In addition, these first distillation residue g is supplied to the 2nd PL distillation tower 7.As the 2nd PL distillation tower 7, used have that theoretical plate number is 8, internal diameter is 200mm and the height continuous still battery tower as 4.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 0.5 the condition in the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, about 180 ℃ head temperature and reflux ratio.The result, by the DPC of top with about 23.5kg/hr acquisition purifying, and high boiling material matter (containing the DPC derivative of the alkyl replacement that is about 350ppm and 40ppm by weight respectively and the DPC of the DPC derivative that bromine replaces) DPC distillation leftover (X1) is discharged at the bottom of tower with 2.5kg/hr.The DPC of described purifying is the high-purity product that contains by weight for the PL of 80ppm.
(PC manufacturing step)
[PC polymerization procedure]
Make PC in the following manner according to schema shown in Figure 5.Promptly in nitrogen atmosphere, by tempering tank 21, purifying DPC and BPA that the weight ratio melting mixing with 0.977 obtains in above-mentioned DPC manufacturing step.Under nitrogen atmosphere and normal pressure, this mixture is by being heated to 130 ℃ raw material supply tube continuous charging to having through adjusting in 210 ℃ the first vertical polymerization tank 22 of temperature.Place the aperture of valve of the polymkeric substance vent line of the bottom that is connected to described groove by adjusting, make fluid level keep constant, thereby obtain 60 minutes average retention time.In addition, when described raw mix is begun to feed in raw material, with aqueous solution form as the cesium carbonate of catalyzer with 0.5 * 10 -6The flow velocity of mole/1 mole of BPA begins without interruption.The liquid polymeric reaction mixture that bottom land is discharged is fed in the second and the 3rd vertical polymerization tank and the 4th horizontal polymerization tank in succession continuously subsequently.During reaction, regulate the fluid level in each groove, thereby obtain 60 minutes average retention time, meanwhile, steam the PL that produces as by product.Adopt corresponding multistage condenser condenses and liquefaction from the first PC evaporation composition p that discharges to the trimerization groove.The part of each gained phlegma is back in each polymerization tank, reclaims remaining phlegma and be stored in PC with in the PL withdrawing can 29.On the other hand, adopt side by side two to freeze the curing of one of condenser by evaporating formation and expellant gas from the 4th polymerizer.Freeze in the condenser by switching to another, fusing gained solid reclaims and is stored in PC with in PL withdrawing can 29 (not shown).
The polymerizing condition of each reactive tank is as follows: and first polymerization tank (210 ℃, 100Torr), second polymerization tank (240 ℃, 15Torr), the trimerization groove (260 ℃, 0.5Torr), the 4th polymerizer (270 ℃, 0.5Torr).
The polymkeric substance that gained is in molten state imports twin screw extruder (Kobe Steel, Ltd (strain) manufacturing; Screw diameter, 0.046m; L/D=40.2) in 32 and granulation, simultaneously being that the amount of 5ppm is to wherein adding butyl p-toluenesulfonate continuously with respect to PC.The viscosity-average molecular weight of gained PC (Mv) be 21000 and initial stage form and aspect (YI) be 1.7.
[PL distilation steps]
The PC evaporation composition p that analysis is reclaimed from the PC polymerization procedure.The result detects the DPC of 5.0 weight %, the BPA of 0.5 weight %, the water of the oligopolymer of 0.3 weight % and 0.2 weight %.
This PC evaporation composition p is by following two distillation tower continuous purifications (a PL distillation tower 30 and the 2nd PL distillation tower 31).The one PL distillation tower 30 is 2 operations at 200Torr and reflux ratio, in view of the above the water that is comprised is steamed as the low overhead product (D6) that boils of PC with a part of PL.Liquid at the bottom of the tower is transported to the 2nd PL distillation tower 31 as fs residue q.The 2nd PL distillation tower 31 is 0.5 operation at 50Torr with reflux ratio, to obtain the PL of purifying by the top.Containing the DPC, the BPA that are respectively 67 weight %, 7 weight % and 4 weight % and the PL distillation leftover (X2) of oligopolymer discharges continuously as liquid at the bottom of the tower.
(the distillation leftover X2 in the PC manufacturing step is delivered to example in the DPC manufacturing step)
PL distillation leftover (X2 with the discharge of the by product PL purification step in the above-mentioned PC manufacturing step; Contain the BPA of DPC, 7 weight % of the PL, the 67 weight % that are respectively 22 weight % and the oligopolymer of 4 weight %) be fed in the DPC distillation tower 6 of above-mentioned DPC manufacturing step.Then, the first distillation leftover g (liquid at the bottom of the tower of a DPC distillation tower 6) is fed in the 2nd DPC distillation tower 7.As a result, almost 100% be included in PL in the PL distillation leftover (X2) by the recovered overhead of a DPC distillation tower 6, make an appointment with the recovered overhead of the DPC of half by the 2nd DPC distillation tower 7.Therefore, only above-mentioned PL distillation leftover (X2) is recycled in the existing particular step and just can reclaims useful composition effectively.
When carrying out aforesaid operations, make DPC and PC in the above described manner.As a result, gained DPC and PC on quality without any problem.
(experimental example 2)
(DPC manufacturing step)
Carry out the DPC manufacturing step according to schema shown in Figure 1.Details is as follows.
[recovery/distilation steps]
To be fed to DPC recovery/distillation tower 8 from the DPC distillation leftover (X1) that the high boiling material matter distilation steps of the DPC manufacturing step the experimental example 1 is discharged, and continuous still battery under the following conditions, with by the recovery liquid d that contain DPC of recovered overhead as overhead product.The overhead product that is reclaimed is recycled to the washing step in the DPC manufacturing step, to realize the raising of yield.On the other hand, high boiling material matter (amount of the DPC derivative that DPC derivative that contained alkyl replaces and bromine replace is respectively the DPC of about 7000ppm and about 800ppm by weight) DPC recovery/distillation leftover (X1 ') is discharged from DPC recovery/distillation tower continuously as liquid at the bottom of the tower.
For DPC recovery/distillation, used have that theoretical plate number is 8, internal diameter is 100mm and the height continuous still battery tower as 3.0m, reflux is equipped with on its top, central authorities have the raw material supply part, and have enrichment region and recovery zone that each free Sulzer Packing (Sumitomo heavy-duty machine industry (strain) manufacturing) fills.Be to distill under 0.5 the condition in the vacuum tightness of 20Torr, about 240 ℃ thermal medium oil temperature, 180 ℃ head temperature and reflux ratio.
Other operation of carrying out in the mode identical with experimental example 1.Therefore, produced purifying DPC (contain and be the PL of 80ppm by weight), thereby produced PC as high-purity product.(distillation leftover in the PC manufacturing step (X2) being delivered to the example of the recovery/distilation steps in the DPC manufacturing step)
With the PL distillation leftover (X2 that discharges in the PL distilation steps in the above-mentioned PC manufacturing step; Contain the BPA of DPC, 7 weight % of the PL, the 67 weight % that are respectively 22 weight % and the oligopolymer of 4 weight %) be fed in the DPC recovery/distillation tower 8 of DPC manufacturing step.As a result, from the recovered overhead of recovery/distillation tower 100% the DPC in this residue of being included in that is included in PL the distillation leftover and about 80 weight % almost.Therefore, only PL distillation leftover X2 is recycled in the existing particular step and just can reclaims useful composition effectively.
When carrying out aforesaid operations, make DPC and PC in the above described manner.As a result, gained DPC and PC on quality without any problem.
(experimental example 3)
(BPA manufacturing step)
Carry out the BPA manufacturing step according to the schema shown in Fig. 2～4.(commodity are called DIAION SK-104 with 60L sulfonic acid type acidic cation-exchange resin, Mitsubishi Chemical's (strain) makes) be filled in the flow type BPA reactor with thermoswitch, 15% sulfo group is neutralized by 4-pyridine ethane mercaptan in the described exchange resin.The liquid mixture that with the mol ratio of PL and acetone is 10: 1 imports in this BPA reactor and reaction at 80 ℃ of flow velocitys with 68.2kg/hr.The transformation efficiency of acetone is 80%.After low boiling substance (unreacted acetone, water and part PL) is discharged with the flow velocity of 5.1kg/hr, reaction mixture is cooled to 50 ℃ and separate out the affixture crystallization.Filter this mixture, the affixture crystallization is separated with mother liquor.Its flow velocity is respectively 16.5kg/hr and 46.5kg/hr.10 weight % of this mother liquor are fed in the mother liquor treatment step, and remaining mother liquor circulates as the part of raw materials that imports synthesis reactor.
The affixture crystallization that so obtains is dissolved in the phenol of supplying with the flow velocity of 27.2kg/hr again.Cooling gained solution to 50 ℃ to separate out crystallization, filters, then so that mother liquor (32.5kg/hr) is separated with affixture crystallization (11.3kg/hr).Low pressure at 0.3mmHg is heated to 180 ℃ with isolating crystallization, to remove PL.Therefore, obtaining flow velocity is the BPA that having of 7.7kg/hr is equal to or greater than 99.95% purity.
On the other hand, as shown in Figure 4, handle the mother liquor that is fed in the mother liquor treatment step with PL vaporizer 13, to steam part PL and condensation mother liquor.Then, the sodium hydroxide of 0.1 weight % is added in the mother liquor, then it is imported the bottom of residue reactor 14 (as decomposition/distillation tower) that has the temperature of the decompression of 50mmHg and 210 ℃ through adjusting.Keep operation described reactor (residence time, 1 hour) under the constant condition in the fluid level that makes the bottom, from this system, discharge liquid at the bottom of the tower in the decomposition/distillation tower with the flow velocity of 0.5kg/hr.In addition, to mix with aforementioned PL from the overhead product that discharge at the top of residue reactor 14, flow velocity with 4.2kg/hr imports this mixture in the flow type regeneration reactor 15 that is filled with 4 L sulfonic acid type acidic cation-exchange resins (commodity are called DIAION SK-104, and Mitsubishi Chemical's (strain) makes).This mixture reacts under 80 ℃ condition.The gained liquid reaction mixture is recycled in the BPA reactor that initial period uses.
Acetone (3.6kg/hr) and PL (18.5kg/hr) are added in the BPA reactor, and additional amount is corresponding with the amount of amount of discharging from system and gained BPA.Therefore, carry out building-up reactions continuously, and operation total system and make BPA continuously.
(DPC distillation leftover (X1) in the DPC manufacturing step and the PL distillation leftover (X2) in the PC manufacturing step are sent to the example of the mother liquor treatment step in the BPA manufacturing step)
Respectively with the flow velocity of 0.11kg/hr and 0.15kg/hr, with the DPC distillation leftover (X1 that discharges in the above-mentioned DPC manufacturing step; Contain the DPC derivative that the alkyl of about 350ppm by weight replaces and the DPC derivative of the bromine replacement of about 40ppm by weight, all the other are DPC) and the PL distillation leftover (X2 that from the by product PL purification step of PC manufacturing step, discharges; Contain the BPA of DPC, 7 weight % of the PL, the 67 weight % that are respectively 22 weight % and the oligopolymer of 4 weight %) be fed in the mother liquor treatment step (step (g)) in the above-mentioned BPA manufacturing step.In this operation, residue reactor 14 is operation (residence time, 1 hour) under the condition that keeps the bottom liquid level constant, and liquid is discharged from system with 0.6kg/hr at the bottom of the tower.
As a result, almost 100% PL and the BPA degradation production that are included in the described distillation leftover have been reclaimed in the top of the residue reactor 14 from the mother liquor treatment step.Therefore, only above-mentioned distillation leftover is recycled in the existing particular step and just can reclaims useful composition effectively.
When carrying out aforesaid operations, make BPA, DPC and PC in the above described manner.As a result, gained BPA, DPC and PC on quality without any problem.
(experimental example 4)
(DPC recovery/distillation leftover (X1 ') in the DPC manufacturing step and the PL distillation leftover (X2) in the PC manufacturing step are sent to the example of the mother liquor treatment step in the BPA manufacturing step)
Respectively with the flow velocity of 0.11kg/hr and 0.15kg/hr, with the DPC distillation leftover of discharging in the above-mentioned DPC manufacturing step (X1 '; Contain the DPC derivative that the alkyl of about 7000ppm by weight replaces and the DPC derivative of the bromine replacement of about 800ppm by weight, all the other are DPC) and the PL distillation leftover (X2 that from the by product PL purification step of PC manufacturing step, discharges; Contain the BPA of DPC, 7 weight % of the PL, the 67 weight % that are respectively 22 weight % and the oligopolymer of 4 weight %) be fed in the mother liquor treatment step (step (g)) in the above-mentioned BPA manufacturing step.In this operation, residue reactor 14 is operation (residence time, 1 hour) under the condition that keeps the bottom liquid level constant, and liquid is discharged from system with 0.6kg/hr at the bottom of the tower.
As a result, almost 100% PL and the BPA degradation production that are included in the described distillation leftover have been reclaimed in the top of the residue reactor 14 from the mother liquor treatment step.Therefore, only distillation leftover is recycled in the existing particular step and just can reclaims useful composition effectively.
When carrying out aforesaid operations, make BPA, DPC and PC in the above described manner.As a result, gained BPA, DPC and PC on quality without any problem.
(experimental example 5)
(the PL distillation leftover (X2) in the PC manufacturing step is delivered to recovery/distilation steps in the DPC manufacturing step, and DPC recovery/distillation leftover (X1 ') is delivered to the example of the mother liquor treatment step in the BPA manufacturing step)
PL distillation leftover (the X2 that discharges in the by product PL purification step with above-mentioned PC manufacturing step; Contain the BPA of DPC, 7 weight % of the PL, the 67 weight % that are respectively 22 weight % and the oligopolymer of 4 weight %) be fed to the DPC recovery/distillation tower 8 in the above-mentioned DPC manufacturing step.To be recycled to the washing step the above-mentioned DPC manufacturing step as the useful component that overhead product is discharged from DPC recovery/distillation tower 8, will be fed to as the DPC recovery/distillation leftover (X1 ') that liquid at the bottom of the tower is discharged from DPC recovery/distillation tower 8 in the mother liquor treatment step (step (g)) the above-mentioned BPA manufacturing step.The useful component that reclaims with this treatment step is a raw material, is used for the synthetic of BPA manufacturing step.When carrying out aforesaid operations, in 400 hours, make BPA, DPC and PC continuously.As a result, gained BPA, DPC and PC on quality without any problem.The height waste that boils can merge in the ejecta by the mother liquor treatment step in the BPA manufacturing step.The amount of described waste significantly descends, and yield then is greatly improved.
Though with reference to specific embodiments the present invention is described in detail,, it will be understood by those skilled in the art that under the premise without departing from the spirit and scope of the present invention, can carry out various changes and correction.
Japanese patent application (the application number: No.2003-297844) that the application submitted to based on August 21st, 2003, Japanese patent application (the application number: No.2003-297719) that on August 21st, 2003 submitted to, Japanese patent application (the application number: No.2003-297832) that on August 21st, 2003 submitted to, Japanese patent application (the application number: No.2003-382667) that on November 12nd, 2003 submitted to, the Japanese patent application of submitting to 2003 1 January 12 (application number: No.2003-382773) and the Japanese patent application (application number of submitting on November 12nd, 2003: No.2003-382646), introduce its full content in this mode by reference.
＜industrial applicibility 〉
According to the present invention, the water content in the by-product phenol is limited in the value of certain limit. Therefore, namely box lunch is with described by-product phenol during as the raw material in diphenyl carbonate manufacturing step or the bisphenol-A manufacturing step a part of, makes efficient and almost do not descend and basically kept.
In addition, the impurity that comprises in the by-product phenol that reclaims in the premature polymerization of aromatic copolycarbonate manufacturing step is the product of the raw material that uses in the diphenyl carbonate manufacturing step and this step. The by-product phenol that therefore, can just will contain these impurity without purifying is as at least a portion of the phenol that uses in the diphenyl carbonate manufacturing step.
On the other hand, the impurity that comprises in the by-product phenol that reclaims in the polymerization of the later stage of aromatic copolycarbonate manufacturing step is hydrolyzed in the bisphenol-A manufacturing step, becomes raw material and the product of this step. In addition, in by-product phenol, comprise hardly alcohol of causing catalyst activity reduction in the bisphenol-A manufacturing step etc. Therefore, comprising the by-product phenol of these impurity can be without at least a portion of purifying namely as the phenol that uses in the bisphenol-A manufacturing step.
In addition, by integrated use diphenyl carbonate manufacturing step, bisphenol-A manufacturing step and aromatic copolycarbonate manufacturing step, can will be purchased the raw material of phenol as the diphenyl carbonate manufacturing, and can distillate composition as the raw material in the bisphenol-A manufacturing step with what produce in the polymerization procedure in the aromatic copolycarbonate manufacturing step.
In addition, if there is following situation, that is, PC was set before or after above-mentioned PL distilation steps stores step, store in the step at this PC, the by-product phenol that reclaims in the evaporation composition of the liquefaction PC before the above-mentioned PL distilation steps and/or the above-mentioned PL distilation steps is stored; DPC is set after above-mentioned DPC distilation steps stores step, store in the step at this DPC, store the diphenyl carbonate that obtains in this DPC distilation steps; And/or the BPA that the mixture of storing bisphenol-A and phenol is set between above-mentioned BPA crystallization/separation step and above-mentioned PC polymerization procedure stores step, so, the quality of the compound that obtains in each step can remain within certain scope, and can carry out continuously later steps, and no matter the step of front how.
In addition, when PL distillation leftover, DPC distillation leftover and/or DPC recovery/distillation leftover are delivered to given step, can utilize the useful component that is included in the described residue fully. Therefore can improve overall efficiency, and reduce carrying capacity of environment.
In addition, vacuum line to the inclination that connects condenser and vacuum equipment is regulated, so that be equal to or less than 1m with the total height of the opposite rising part that has a down dip, at this moment, can reduce the liquid substance that is trapped in described rising part and the amount of solid matter, can also prevent that described pipeline from being stopped up fully or the pressure loss is excessive.

Claims (44)

1. the manufacture method of aromatic copolycarbonate, this method comprises:
The diphenyl carbonate manufacturing step wherein is used as the raw material of making diphenyl carbonate with phenol and at least a carbonyl compound;
And/or the dihydroxyphenyl propane manufacturing step, wherein phenol and acetone are used as the raw material of making dihydroxyphenyl propane;
And the aromatic copolycarbonate manufacturing step, be raw material wherein with above-mentioned diphenyl carbonate and dihydroxyphenyl propane, make aromatic copolycarbonate by the aromatic copolycarbonate polymerization procedure, and reclaim by-product phenol,
It is characterized in that, the amount of the water that comprised in the by-product phenol that reclaims in the described aromatic copolycarbonate manufacturing step is adjusted to is equal to or less than 0.2 weight %, and with the raw material of described phenol as above-mentioned diphenyl carbonate manufacturing step and/or dihydroxyphenyl propane manufacturing step.
2. the manufacture method of aromatic copolycarbonate as claimed in claim 1 is characterized in that, described diphenyl carbonate manufacturing step is to comprise the reactions steps of making diphenyl carbonate and the step of diphenyl carbonate distilation steps.
3. the manufacture method of aromatic copolycarbonate as claimed in claim 1, it is characterized in that, described dihydroxyphenyl propane manufacturing step comprises bisphenol-a reaction step, dihydroxyphenyl propane low boiling substance removal step and dihydroxyphenyl propane crystallization/separation step, and comprises that further described dihydroxyphenyl propane low boiling substance is removed the low overhead product that boils of the dihydroxyphenyl propane of discharging in the step carries out dihydroxyphenyl propane/water sepn step to reclaim the step of phenol.
4. the manufacture method of aromatic copolycarbonate as claimed in claim 1, it is characterized in that, the step that reclaims by-product phenol in the described aromatic copolycarbonate manufacturing step is following steps: make the aromatic carbonate that obtains from described aromatic carbonate polymerization procedure flash to branch liquefaction, and it is carried out the phenol distillation step, hang down the overhead product that boils from this aromatic carbonate evaporation composition, to remove aromatic carbonate, and reclaim by-product phenol in view of the above.
5. the manufacture method of aromatic copolycarbonate as claimed in claim 4 is characterized in that, the phenol concentration in the low overhead product that boils of the polycarbonate of removing in described phenol distillation step is 50 weight %～99.8 weight %.
6. the manufacture method of aromatic copolycarbonate as claimed in claim 4 is characterized in that, described diphenyl carbonate manufacturing step has the diphenyl carbonate washing step between described diphenyl carbonate reaction step and diphenyl carbonate distilation steps.
7. the manufacture method of aromatic copolycarbonate as claimed in claim 4 is characterized in that, the low overhead product that boils of aromatic carbonate that produces in the described phenol distillation step is delivered to described dihydroxyphenyl propane/water sepn step.
8. the manufacture method of aromatic copolycarbonate as claimed in claim 1 or 2 is characterized in that, is lower than 10ppm by weight as the content of pyruvic alcohol in the phenol of the raw material of described dihydroxyphenyl propane manufacturing step.
9. the manufacture method of aromatic copolycarbonate as claimed in claim 3, wherein, employed acid catalyst is with the compound modified sulfonic acid ion exchange resin with sulfydryl in described bisphenol-a reaction step.
10. the manufacture method of aromatic copolycarbonate as claimed in claim 4, it is characterized in that, before described phenol distillation step and/or aromatic carbonate is set afterwards stores step, store in the step at described aromatic carbonate, to carry out the by-product phenol storage that the preceding aromatic carbonate of described phenol distillation step flashes to branch liquefaction thing and/or reclaims in described phenol distillation step, and the aromatic carbonate hold tank that capacity is satisfied the condition of following formula (1) is used for described aromatic carbonate storage step:
10≤(Vc/Fc)≤100 (1)
Wherein, Vc represents the capacity of described aromatic carbonate hold tank, and its unit is m 3, Fc represents that aromatic carbonate flashes to the feed rate of branch liquefaction thing or by-product phenol, its unit is m 3/ hour.
11. the manufacture method of aromatic copolycarbonate as claimed in claim 2, it is characterized in that, after described diphenyl carbonate distilation steps, store the diphenyl carbonate of the diphenyl carbonate that obtains in the described diphenyl carbonate distilation steps and store step, and the diphenyl carbonate hold tank that capacity is satisfied the condition of following formula (2) is used for described diphenyl carbonate storage step:
10≤(Vd/Fd)≤100 (2)
Wherein, Vd represents the capacity of diphenyl carbonate hold tank, and its unit is m 3, Fd represents the feed rate of diphenyl carbonate, its unit is m 3/ hour.
12. the manufacture method of aromatic copolycarbonate as claimed in claim 3 is characterized in that, stores the dihydroxyphenyl propane of the mixture of dihydroxyphenyl propane and phenol and store step between described dihydroxyphenyl propane crystallization/separation step and above-mentioned aromatic carbonate polymerization procedure.
13. the manufacture method of aromatic copolycarbonate as claimed in claim 12 is characterized in that, the dihydroxyphenyl propane hold tank that capacity is satisfied the condition of following formula (3) is used for described dihydroxyphenyl propane storage step:
10≤(Vb/Fb)≤1000 (3)
Wherein, Vb represents the capacity of described dihydroxyphenyl propane hold tank, and its unit is m 3, Fb represents to be added into the feed rate of the dihydroxyphenyl propane in the described aromatic carbonate polymerization procedure, and its unit is m 3/ hour.
14. the manufacture method of aromatic copolycarbonate as claimed in claim 12 is characterized in that, the bisphenol a/phenol mixture of storing in described dihydroxyphenyl propane storage step is any one of following form: the crystallization of the affixture of dihydroxyphenyl propane and phenol; The slurry that contains the affixture of dihydroxyphenyl propane and phenol; Or the liquid mixture of dihydroxyphenyl propane and phenol.
15. the manufacture method of aromatic copolycarbonate as claimed in claim 12 is characterized in that, carries out neutralization procedure between described dihydroxyphenyl propane crystallisation step and aromatic carbonate polymerization procedure or before these steps.
16. the manufacture method of aromatic copolycarbonate as claimed in claim 12 is characterized in that, intermittently carries out from described bisphenol-a reaction step to the step of dihydroxyphenyl propane crystallisation step, described aromatic carbonate polymerization procedure carries out continuously.
17. the manufacture method of aromatic copolycarbonate as claimed in claim 4 is characterized in that, the phenol distillation residue that produces in the described phenol distillation step is delivered to described diphenyl carbonate distilation steps.
18. the manufacture method of aromatic copolycarbonate as claimed in claim 4, it is characterized in that, described diphenyl carbonate manufacturing step comprises the diphenyl carbonate recovery/distilation steps that reclaims diphenyl carbonate from the diphenyl carbonate distillation leftover that described diphenyl carbonate distilation steps produces, and
The phenol distillation residue that produces in the described phenol distillation step is delivered to described diphenyl carbonate distilation steps and/or diphenyl carbonate recovery/distilation steps.
19. the manufacture method of aromatic copolycarbonate as claimed in claim 4, it is characterized in that, described dihydroxyphenyl propane manufacturing step may further comprise the steps, in this step, the part or all of mother liquor that described dihydroxyphenyl propane crystallization/separation step is discharged is delivered to dihydroxyphenyl propane mother liquor treatment step to reduce the amount of by product in this mother liquor, in then this mother liquor being made as dihydroxyphenyl propane as part or all of the phenol of raw material, and
The diphenyl carbonate distillation leftover that produces in the phenol distillation residue that produces in the described phenol distillation step and/or the described diphenyl carbonate distilation steps is delivered to described dihydroxyphenyl propane mother liquor treatment step in the described dihydroxyphenyl propane manufacturing step.
20. the manufacture method of aromatic copolycarbonate as claimed in claim 4 is characterized in that, following material is delivered to described dihydroxyphenyl propane mother liquor treatment step in the described dihydroxyphenyl propane manufacturing step; Described material is the phenol distillation residue that produces in the described phenol distillation step, and/or the diphenyl carbonate distillation leftover that produces in the described diphenyl carbonate distilation steps, and/or the diphenyl carbonate recovery/distillation leftover that produces in the described diphenyl carbonate recovery/distilation steps.
21. the manufacture method of aromatic copolycarbonate as claimed in claim 4, it is characterized in that, the phenol distillation residue that produces in the described phenol distillation step is delivered to described diphenyl carbonate distilation steps, then the distillation leftover that produces in the described diphenyl carbonate distilation steps is delivered to described dihydroxyphenyl propane mother liquor treatment step.
22. the manufacture method of aromatic copolycarbonate as claimed in claim 4, it is characterized in that, the phenol distillation residue that produces in the described phenol distillation step is delivered to described diphenyl carbonate distilation steps and/or benzol carbonate recovery/distilation steps, then the diphenyl carbonate distillation leftover and/or the diphenyl carbonate recovery/distillation leftover that produce in the described diphenyl carbonate distilation steps are delivered to described dihydroxyphenyl propane mother liquor treatment step.
23. the manufacture method of aromatic copolycarbonate as claimed in claim 19, it is characterized in that, described dihydroxyphenyl propane mother liquor treatment step comprises: add alkaline matter to part or all of mother liquor, heat this mixture to produce the derivative of phenol and phenol, under the assistance of acid catalyst or alkaline catalysts, make the derivatives reaction of this phenol and phenol then, obtain dihydroxyphenyl propane in view of the above.
24. the manufacture method of aromatic copolycarbonate as claimed in claim 23 is characterized in that, described alkaline matter is sodium hydroxide or potassium hydroxide.
25. the manufacture method of aromatic copolycarbonate as claimed in claim 2, it is characterized in that, for the distillation tower in the described diphenyl carbonate distilation steps is provided for the condenser of condensation overhead product, the vacuum-lines that is used for the vacuum apparatus of system decompression and connects described condenser and described vacuum apparatus, and
Described vacuum-lines is had a down dip to described vacuum apparatus side direction by described condenser side, and the total height of the part that is risen to the described vacuum apparatus side direction by described condenser side is equal to or less than 1m.
26. the manufacture method of aromatic copolycarbonate as claimed in claim 2, it is characterized in that, the poly-unit that uses for the step of the evaporation of the liquefaction polycarbonate in described polycarbonate polymerization step composition is provided for condenser, the vacuum apparatus that be used for paradigmatic system decompression and the vacuum-lines that connect described condenser and described vacuum apparatus of condensation as the polycarbonate evaporation composition of overhead product, and
Described vacuum-lines is had a down dip to described vacuum apparatus side direction by described condenser side, and the total height of the part that is risen to the described vacuum apparatus side direction by described condenser side is equal to or less than 1m.
27. the manufacture method of aromatic copolycarbonate as claimed in claim 2, it is characterized in that, for the distillation tower in the described phenol distillation step is provided for the condenser of condensation overhead product, the vacuum-lines that is used for the vacuum apparatus of system decompression and connects described condenser and described vacuum apparatus, and
Described vacuum-lines is had a down dip to described vacuum apparatus side direction by described condenser side, and the total height of the part that is risen to the described vacuum apparatus side direction by described condenser side is equal to or less than 1m.
28. the manufacture method of aromatic copolycarbonate as claimed in claim 25, it is characterized in that, described vacuum-lines has following equipment, and this equipment is used for making its temperature be not less than the fusing point of the overhead product of being discharged by described distillation tower and/or poly-unit in the described pipeline of heat tracing inside.
29. the manufacture method of aromatic copolycarbonate as claimed in claim 25 is characterized in that, provides at least one leakage fluid dram in the described vacuum apparatus side of described vacuum-lines.
30. the manufacture method of aromatic copolycarbonate as claimed in claim 25 is characterized in that, provides supplying opening at the described condenser side of described vacuum-lines, described supplying opening is used to supply heating fluid.
31. the manufacture method of aromatic copolycarbonate as claimed in claim 30 is characterized in that, by described supplying opening supply heating fluid, to clean described vacuum-lines.
32. the manufacture method of aromatic copolycarbonate as claimed in claim 31 is characterized in that, described heating fluid comprises at least a in water vapor, phenol and the nitrogen.
33. manufacture method as each described aromatic copolycarbonate of claim 31, it is characterized in that, as the phenol of the raw material in the described diphenyl carbonate manufacturing step is the phenol that contains by weight for the cresols of 20ppm～1000ppm and/or xylenol, and
The phenol that produces in the described polymerization procedure in the described aromatic copolycarbonate manufacturing step is used as at least a portion that is used as the phenol of raw material in the described dihydroxyphenyl propane manufacturing step.
34. the manufacture method of aromatic copolycarbonate as claimed in claim 33 is characterized in that, is used as the cresols in the phenol of raw material and/or the content of xylenol in the described dihydroxyphenyl propane manufacturing step and is lower than 20ppm by weight.
35. the manufacture method of aromatic copolycarbonate as claimed in claim 33, it is characterized in that, the phenol that produces in the described polymerization procedure in described aromatic copolycarbonate manufacturing step is through after the step of removing water, as at least a portion that is used as the phenol of raw material in the described dihydroxyphenyl propane manufacturing step.
36. the manufacture method of aromatic copolycarbonate as claimed in claim 35, it is characterized in that, described dihydroxyphenyl propane manufacturing step comprises bisphenol-a reaction step, dihydroxyphenyl propane low boiling substance removal step and dihydroxyphenyl propane crystallization/separation step, and comprise that further described dihydroxyphenyl propane low boiling substance is removed the low overhead product that boils of the described dihydroxyphenyl propane of discharging in the step carries out the step of dihydroxyphenyl propane/water sepn step with recovery phenol, and
The step of described removal water is the water sepn step in the described dihydroxyphenyl propane manufacturing step.
37. the manufacture method of aromatic copolycarbonate as claimed in claim 35 is characterized in that, after the step of described removal water, separates the dihydroxyphenyl propane/high boiling material matter separating step of the boiling point composition higher than phenol.
38. the manufacture method of aromatic copolycarbonate as claimed in claim 37, it is characterized in that, described dihydroxyphenyl propane manufacturing step may further comprise the steps: the mother liquor that described dihydroxyphenyl propane crystallization/separation step is discharged partly or entirely deliver to dihydroxyphenyl propane mother liquor treatment step, to reduce the amount of the by product in this mother liquor, then this mother liquor is made part or all of phenol of raw material as dihydroxyphenyl propane; And, described dihydroxyphenyl propane/high boiling material matter is removed the boiling point one-tenth higher than phenol that obtains in the step is distributed to described dihydroxyphenyl propane mother liquor treatment step.
39. the manufacture method of aromatic copolycarbonate as claimed in claim 1, it is characterized in that, with the 50 weight %～95 weight % of the phenol that produces as by product in the described aromatic copolycarbonate manufacturing step as at least a portion that is used as the phenol of raw material in the described diphenyl carbonate manufacturing step, and with the 50 weight %～5 weight % of the phenol that produces as by product in the described aromatic copolycarbonate manufacturing step as at least a portion that is used as the phenol of raw material in the described dihydroxyphenyl propane manufacturing step.
40. the manufacture method of aromatic copolycarbonate as claimed in claim 39, it is characterized in that, with the 50 weight %～70 weight % of the phenol that produces as by product in the described aromatic copolycarbonate manufacturing step as at least a portion that is used as the phenol of raw material in the described diphenyl carbonate manufacturing step, and with the 50 weight %～30 weight % of the phenol that produces as by product in the described aromatic copolycarbonate manufacturing step as at least a portion that is used as the phenol of raw material in the described dihydroxyphenyl propane manufacturing step.
41. the manufacture method of aromatic copolycarbonate as claimed in claim 1, it is characterized in that, polymerization procedure in the described aromatic copolycarbonate manufacturing step is made of 3 polymerization tanks at least, in above-mentioned polymerization tank, to be used as at least a portion of the phenol that uses the described diphenyl carbonate manufacturing step from the by-product phenol of described first groove or the recovery of first and second grooves, and in above-mentioned polymerization tank, will be after described second groove or the later polymerization tank of described three-flute the by-product phenol that reclaims as at least a portion of the phenol that uses in the described dihydroxyphenyl propane manufacturing step.
42. the manufacture method of aromatic copolycarbonate as claimed in claim 39, wherein, the by-product phenol that uses in the described diphenyl carbonate manufacturing step comprises the boiling point higher-boiling compound higher than diphenyl carbonate that is up to 1.0 weight %.
43. the manufacture method of aromatic copolycarbonate as claimed in claim 39, wherein, the one or more described polymerization tank that obtains the by-product phenol that uses in the described diphenyl carbonate manufacturing step has the reflux that is used for the refluxed evaporator composition.
44. the manufacture method of aromatic copolycarbonate as claimed in claim 39, wherein, when described carbonyl compound is dialkyl carbonate and/or carbonate alkyl aryl ester, and when the phenol that produces as by product in the described aromatic copolycarbonate manufacturing step is used as part of raw materials in the described dihydroxyphenyl propane manufacturing step, should comprise as phenol of raw material by weight for the dialkyl carbonate that is equal to or less than 20ppm, carbonate alkyl aryl ester and available from the alkyl alcohol of dialkyl carbonate and/or carbonate alkyl aryl ester.
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US9546249B2 (en) * 2012-11-17 2017-01-17 Mitsubishi Gas Chemical Company, Inc. Process for preparing highly polymerized aromatic polycarbonate resin
CN110538481B (en) * 2019-10-11 2021-02-02 中国科学院过程工程研究所 Phenol continuous extraction system, polycarbonate resin production system comprising phenol continuous extraction system and production method
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